Catalysts — Open Access Journal of Catalysis

Terpenes are valuable starting materials for the synthesis of molecules that are of interest to the flavor, fragrance, and pharmaceutical industries. However, most processes involve the use of mineral acids or homogeneous Lewis acid catalysts. Here, we report results obtained in the liquid-phase reaction of citronellal with anilines under heterogeneous catalysis conditions to give tricyclic compounds with interesting pharmacological activity. The terpenic aldehyde could be converted into octahydroacridines with a 92% yield through an intramolecular imino Diels–Alder reaction of the imine initially formed in the presence of an acidic clay such as Montmorillonite KSF. Selectivity to the desired product strongly depended on the acid sites distribution, with Brønsted acids favoring selectivity to octahydroacridine and formation of the cis isomer. Pure Lewis acids such as silica–alumina with a very low amount of alumina gave excellent results with electron-rich anilines like toluidine and p-anisidine. This protocol can be applied starting directly from essential oils such as kaffir lime oil, which has a high citronellal content. Full article

Titanium dioxide (TiO₂) photocatalysis is one of the most commonly studied advanced oxidation processes (AOPs) for the mineralization of deleterious and recalcitrant compounds present in wastewater as it is stable, inexpensive, and effective. Out of all, doping with metal and non-metals, and the heterojunction with another semiconductor were proven to be efficient methods in enhancing the degradation of organic pollutants under ultraviolet (UV) and visible light. However, complex degradation processes in the treatment of an actual wastewater are difficult to model and optimize. In the present study, the application of a modified photocatalyst, Ag/TiO₂/Fe₂O₃, for the degradation of an actual confectionery wastewater was investigated. Factorial studies and statistical design of experiments using the Box-Behnken method along with response surface methodology (RSM) were employed to identify the individual and cross-factor effects of independent parameters, including light wavelength (nm), photocatalyst concentration (g/L), initial pH, and initial total organic carbon (TOC) concentration (g/L). The maximum TOC removal at optimum conditions of light wavelength (254 nm), pH (4.68), photocatalyst dosage (480 mg/L), and initial TOC concentration (11,126.5 mg/L) was determined through the numerical optimization method (9.78%) and validated with experimental data (9.42%). Finally, the first-order rate constant with respect to TOC was found to be 0.0005 min⁻¹ with a residual value of 0.998. Full article

Cuprous oxide nanoparticles (Cu₂O NPs) were dispersed into a graphene oxide (GO) solution to form a homogeneous Cu₂O-GO dispersion. After this, the cuprous oxide nanoparticles were functionalized to electrochemically reduce the graphene oxide decorated glassy carbon electrode (Cu₂O-ErGO/GCE). This was prepared by coating the Cu₂O-GO dispersion onto the surface of the glassy carbon electrode (GCE), which was followed by a potentiostatic reduction process. An irreversible two-electron reaction of uric acid (UA) was observed at the voltammetric sensor. Moreover, the high concentrations of dopamine (DA) and ascorbic acid (AA) hardly affected the peak current of UA, which suggested that Cu₂O-ErGO/GCE have excellent selectivity for UA. This is probably because the response peaks of the three compounds are well-separated from each other. The oxidation peak current was proportional to the concentration of UA in the ranges of 2.0 nM−0.6 μM and 0.6 μM−10 μM, respectively, with a low limit of detection (S/N = 3, 1.0 nM) after an accumulation time of 120 s. Cu₂O-ErGO/GCE was utilized for the rapid detection of UA in human blood serum and urine samples with satisfactory results. Full article

Water-borne virus pollution has caused great harm and attracted widespread attention in many countries. Visible-light-driven photocatalysis is considered as a promising process for disinfection. In this study, Ag₃PO₄/g-C₃N₄ (AgCN) composites were synthesized by hydrothermal method. The photocatalytic disinfection was investigated using bacteriophage f2 as the model virus. Moreover, the effects of pH and humic acid on photocatalytic disinfection were studied. Meanwhile, the mechanism of enhanced disinfection by Ag₃PO₄/g-C₃N₄ was systematically investigated by radical scavenger experiments. The results show that Ag₃PO₄ particles were uniformly distributed on g-C₃N₄ sheets. By means of photoluminescence spectrometer analysis, it is confirmed that a lower carrier recombination rate for Ag₃PO₄/g-C₃N₄ was achieved compared with Ag₃PO₃ and g-C₃N₄. Meanwhile, complete inactivation of f2 with concentration of 3 × 10⁶ PFU/mL was reached within 80 min in the presence of Ag₃PO₄/g-C₃N₄ composite. The pH had little effect on removal efficiency overall, while the existence of humic acid resulted in a significant negative effect on the inactivation of f2 due to the optical shielding and absorption of humic acid. Recycling tests of Ag₃PO₄/g-C₃N₄ confirmed that Ag₃PO₄/g-C₃N₄ presented superior stability. The results from radical scavenger experiments indicated that holes (h⁺) and hydroxyl radicals (·OH) played important roles in photocatalytic disinfection process. Full article

Developing photocatalysts with molecular recognition function is very interesting and desired for specific applications in the environmental field. Copper ferrite/N-doped graphene (CuFe₂O₄/NG) hybrid catalyst was synthesized and characterized by surface photovoltage spectroscopy, X-ray powder diffraction, transmission electron microscopy, Raman spectroscopy, UV–Vis near-infrared diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The CuFe₂O₄/NG catalyst can recognize ammonia from rhodamine B (RhB) in ammonia-RhB mixed solution and selectively degrade ammonia under visible near-infrared irradiation. The degradation ratio for ammonia reached 92.6% at 6 h while the degradation ratio for RhB was only 39.3% in a mixed solution containing 100.0 mg/L NH₃-N and 50 mg/L RhB. Raman spectra and X-ray photoelectron spectra indicated ammonia adsorbed on CuFe₂O₄ while RhB was adsorbed on NG. The products of oxidized ammonia were detected by gas chromatography, and results showed that N₂ was formed during photocatalytic oxidization. Mechanism studies showed that photo-generated electrons flow to N-doped graphene following the Z-scheme configuration to reduce O₂ dissolved in solution, while photo-generated holes oxidize directly ammonia to nitrogen gas. Full article

Covalent organic frameworks (COFs) are defined as highly porous and crystalline polymers, constructed and connected via covalent bonds, extending in two- or three-dimension. Compared with other porous materials such as zeolite and active carbon, the versatile and alternative constituent elements, chemical bonding types and characteristics of ordered skeleton and pore, enable the rising large family of COFs more available to diverse applications including gas separation and storage, optoelectronics, proton conduction, energy storage and in particular, catalysis. As the representative candidate of next-generation catalysis materials, because of their large surface area, accessible and size-tunable open nano-pores, COFs materials are suitable for incorporating external useful active ingredients such as ligands, complexes, even metal nanoparticles deposition and substrate diffusion. These advantages make it capable to catalyze a variety of useful organic reactions such as important C-C bond formations. By appropriate pore-engineering in COFs materials, even enantioselective asymmetric C-C bond formations could be realized with excellent yield and ee value in much shorter reaction time compared with their monomer and oligomer analogues. This review will mainly introduce and discuss the paragon examples of COFs materials for application in C-C bond formation reactions for the organic synthetic purpose. Full article

Tetraethylammonium tetrachloroferrate catalyzes the photooxidation of cyclohexane heterogeneously, exhibiting significant photocatalysis even in the visible portion of the spectrum. The photoproducts, cyclohexanol and cyclohexanone, initially develop at constant rates, implying that the ketone and the alcohol are both primary products. The yield is improved by the inclusion of 1% acetic acid in the cyclohexane. With small amounts of catalyst, the reaction rate increases with the amount of catalyst employed, but then passes through a maximum and decreases, due to increased reflection of the incident light. The reaction rate also passes through a maximum as the percentage of dioxygen above the sample is increased. This behavior is due to quenching by oxygen, which at the same time is a reactant. Under one set of reaction conditions, the photonic efficiency at 365 nm was 0.018 mol/Einstein. Compared to TiO₂ as a catalyst, Et₄N[FeCl₄] generates lower yields at wavelengths below about 380 nm, but higher yields at longer wavelengths. Selectivity for cyclohexanol is considerably greater with Et₄N[FeCl₄], and oxidation does not proceed past cyclohexanone. Full article

In recent years, groundwater contamination caused by dyes has become an important problem. They enter into wastewater as a result of the textile, automotive, or cosmetics industries. For this reason, new methods are being sought, which would aid at the removal of dye impurities with high efficiency and also would be relatively cheap. In the presented study synthesized TiO₂-ZrO₂ (with TiO₂:ZrO₂ molar ratio of 8:2) and TiO₂-ZrO₂-SiO₂ (with TiO₂:ZrO₂:SiO₂ molar ratio of 8:1:1) oxide materials were used as supports for enzyme immobilization. Effective synthesis of the carriers was confirmed by results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), low-temperature nitrogen sorption and Fourier transform infrared spectroscopy (FTIR). The materials achieve high immobilization efficiency of the laccases from Trametes versicolor (83% and 96% for TiO₂-ZrO₂-laccase and TiO₂-ZrO₂-SiO₂-laccase, respectively). The effect of selected dye concentrations, pH, temperature, and reusability were also tested. The obtained results showed that after removal of textile dyes, such as Alizarin Red S (ARS), Remazol Brilliant Blue R (RBBR), and Reactive Black 5 (RB5), under optimal process conditions, which were pH 5 and 25 °C, from dye solution of 5 mg/L degradation efficiency reached 100%, 91%, and 77%, respectively, suggesting synergistic mechanism of degradation by simultaneous sorption and catalytic action. Finally, reduction of chemical oxygen demand (COD) of the solution after treatment indicated lower mixture toxicity and effective dye degradation. Full article

In this study, chitosanase cloning from Streptomyces albolongus was fermented and purified by a Ni-NTA column. Fe₃O₄-SiO₂ magnetite nanoparticles (MNPs) were synthesized by the co-precipitation method coating with silica via a sol-gel reaction and were then amino functioned by treating with 3-aminopropyltriethoxysilane. Chitosanases were immobilized onto the surface of MNPs by covalent bonding (MNPs@chitosanase). Transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FT–IR), and magnetic measurements were used to illustrate the MNPs and immobilized chitosanase. The optimal conditions of immobilization were studied. The thermal, pH, and stabilities of immobilized chitosanase were tested and the results showed that the stabilities were significantly enhanced compared with free chitosanase. After being recycled 10 times, the residual activity of the immobilized chitosanase was 43.7% of the initial activity. Full article

ω-Aminododecanoic acid is considered as one of the potential monomers of Nylon 12, a high-performance member of the bioplastic family. The biosynthesis of ω-aminododecanoic acid from renewable sources is an attractive process in the polymer industry. Here, we constructed three artificial self-sufficient P450s (ArtssP450s) using CYP153A13 from Alcanivorax borkumensis and cytochrome P450 reductase (CPR) domains of natural self-sufficient P450s (CYP102A1, CYP102A5, and 102D1). Among them, artificial self-sufficient P450 (CYP_153A13BM3_CPR) with CYP102A1 CPR showed the highest catalytically activity for dodecanoic acid (DDA) substrate. This form of ArtssP450 was further co-expressed with ω-TA from Silicobacter pomeroyi and AlkJ from Pseudomonas putida GPo1. This single-cell system was used for the biotransformation of dodecanoic acid (DDA) to ω-aminododecanoic acid (ω-AmDDA), wherein we could successfully biosynthesize 1.48 mM ω-AmDDA from 10 mM DDA substrate in a one-pot reaction. The productivity achieved in the present study was five times higher than that achieved in our previously reported multistep biosynthesis method (0.3 mM). Full article

A series of composites of Mn-Fe-Ce/GO-x have been synthesized by a hydrothermal method. Their performance in simultaneously performing the catalytic oxidation of Hg⁰ and the selective catalytic reduction of nitrogen oxides (NO_x) in the same temperature range were investigated. In order to investigate the physicochemical properties and surface reaction, basic tests, including Brunauer-Emmett-Teller (BET), XRD, scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) were selected. The results indicate that the active components deposited on graphene play an important role in the removal of mercury and NO_x, with different valences. Especially, the catalyst of Mn-Fe-Ce/GO-20% possesses an excellent efficiency in the temperature range of 170 to 250 °C. Graphene has a huge specific surface area and good mechanical property; thus, the active components of the Mn-Fe-Ce catalyst can be highly dispersed on the surface of graphene oxide. In addition, the effects of O₂, H₂O, NO and SO₂ on the removal efficiency of Hg⁰ were examined in flue gas. Furthermore, the regeneration experiments conducted by thermal methods proved to be promising methods. Full article

The hydroprocessing of substituted naphthalenes and light cycle oil (LCO) over bimetallic Ni-W-S and Ni-Mo-S catalysts that were obtained by decomposition of [N(n-Bu)₄]₂[Ni(MeS₄)₂] (Me = W, Mo) complexes in situ in the pores of mesoporous aromatic frameworks (PAFs) during the reaction, was studied. The promotion of acid-catalyzed processes by PAF-AlCl₃, synthesized by impregnation of a PAF with AlCl₃ from its toluene solution, was investigated. It has been found that Ni-W-S catalytic systems were more active in the hydrodearomatization reactions, while Ni-Mo-S catalytic systems were more active in hydrodesulfurization and hydrocracking reactions. The introduction of sulfur into the reaction medium enhanced the activity of the catalysts and the presence of PAF-AlCl₃ led to an acceleration of the hydrocracking processes. Full article

The performance of fixed-bed reactors with structured catalysts depends heavily on the gas–liquid–solid contacting pattern. For a broad range of flow conditions, the liquid phase does not cover the solid surface of the packing homogeneously; this is known as partial wetting. The wetting fraction in solid foams was obtained using a modified electrochemical measurement method with adaption of the limiting-current technique in different pre-wetting scenarios. The external wetting fraction, which is defined as fraction of the external solid-foam area covered by the liquid phase to the total external solid-foam area, is directly linked to the overall rate of reaction through the overall liquid mass transfer rate. The wetting fraction decreased with an increase in foam density, a process which was related to decreasing the strut thickness, increasing foam surface area, and consequently, decreasing the wetted area. Additionally, the results indicate that a better distribution of liquid and an increased wetting fraction occurred when a spray nozzle distributor was applied. A new wetting correlation for solid foams is proposed to estimate the wetting fraction with consideration of foam morphology and flow regime. Full article

Electrochemical technology has been proposed as an alternative or complementary method to classical inorganic synthesis for the fabrication of effective metallic solid catalysts. Microemulsion-based electrodeposition is a novel, fast, and one-step procedure to obtain mesoporous catalysts with extraordinarily effective areas, which can be used in heterogeneous catalysis for degradation of pollutants and clean energy production. The fabrication process involves conducting microemulsions containing ionic species (dissolved in aqueous solutions) as precursors of the metallic catalysts. The presence of nanometric droplets of organic or ionic-liquid components in the microemulsion defines the mesoporosity of the catalysts during a one-step electrodeposition process. This method also allows the fabrication of metal catalysts as supported mesoporous films or mesoporous nanowires with very high effective areas. Additionally, reactants have excellent accessibility to the overall surface of the catalysts. The different catalysts fabricated with the help of this technology have been tested for competitive degradation of organic pollutants and anodes' materials for fuel cell devices. Full article

Nowadays, the controllable synthesis of stable hierarchical metal–organic frameworks (MOFs) is very important for practical applications, especially in catalysis. Herein, a well-known chromium–benzenedicarboxylate metal–organic framework, MIL-101(Cr), with a stable hierarchical structure, was produced by using phenylphosphonic acid (PPOA) as a modulator via the hydrothermal method. The presence of phenylphosphonic acid could create structural defects and generate larger mesopores. The synthesized hierarchical MIL-101(Cr) possesses relatively good porosity, and the larger mesopores had widths of 4–10 nm. The hierarchical MIL-101(Cr) showed significant improvement for catalytic activity in the oxidation of indene. Further, the presence of a hierarchical structure could largely enhance large dye molecule uptake properties by impregnating. Full article

The terpolymerization of propylene oxide (PO), CO₂, and a lactone is one of the prominent sustainable procedures for synthesizing thermoplastic materials at an industrial scale. Herein, the one-pot terpolymerization of PO, CO₂, and β-butyrolactone (BBL) was achieved for the first time using a heterogeneous nano-sized catalyst: zinc glutarate (ZnGA-20). The reactivity of both PO and BBL increased with the CO₂ pressure, and the polyester content of the terpolymer poly (carbonate-co-ester) could be tuned by controlling the infeed ratio of PO to BBL. When the polyester content increased, the thermal stability of the polymers increased, whereas the glass transition temperature (T_g) decreased. Full article

In this work, we have synthesized the rod-on-rod–like α-FeOOH/α-AgVO₃ nanocomposite photocatalysts with the different amounts of solvothermally synthesized α-FeOOH nanorods via a simple co-precipitation method. The as-synthesized photocatalysts were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, UV−Visible diffuse reflectance spectroscopy, scanning electron microscopy (SEM), element mapping, high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS) analysis. The observed SEM images show that both α-AgVO₃ and α-FeOOH exhibits the rod-shaped morphology with nano size. Furthermore, the photocatalytic activities of the obtained photocatalysts were evaluated towards the degradation of Rhodamine B (RhB) under visible-light irradiation. It is demonstrated that the 3 mg α-FeOOH added to the α-FeOOH/α-AgVO₃ nanocomposite exhibited an enhanced photocatalytic performance as compared with the pure α-AgVO₃ and α-FeOOH. This significant improvement can be attributed to the increased photo-excited electron-hole pair separation efficiency, large portion of visible-light absorption ability and the reduced recombination of the electron-hole pair. The recycling test revealed that the optimized nanocomposite exhibited good photostability and reusability properties. In addition, the believable photodegradation mechanism of RhB using α-FeOOH/α-AgVO₃ nanocomposite is proposed. Hence, the developed α-FeOOH/α-AgVO₃ nanocomposite is a promising material for the degradation of organic pollutants in an aqueous environment. Full article