Catalysts — Open Access Journal of Catalysis

Myceliophthora thermophyla is a thermophilic industrially relevant fungus that secretes an assortment of hydrolytic and oxidative enzymes for lignocellulose degradation. Among them is glyoxal oxidase (MtGLOx), an extracellular oxidoreductase that oxidizes several aldehydes and α-hydroxy carbonyl substrates coupled to the reduction of O₂ to H₂O₂. This copper metalloprotein belongs to a class of enzymes called radical copper oxidases (CRO) and to the “auxiliary activities” subfamily AA5_1 that is based on the Carbohydrate-Active enZYmes (CAZy) database. Only a few members of this family have been characterized to date. Here, we report the recombinant production, characterization, and structure-function analysis of MtGLOx. Electron Paramagnetic Resonance (EPR) spectroscopy confirmed MtGLOx to be a radical-coupled copper complex and small angle X-ray scattering (SAXS) revealed an extended spatial arrangement of the catalytic and four N-terminal WSC domains. Furthermore, we demonstrate that methylglyoxal and 5-hydroxymethylfurfural (HMF), a fermentation inhibitor, are substrates for the enzyme. Full article

Carbon nanomaterials are potential materials with their intrinsic structure and property in energy conversion and storage. As the electrocatalysts, graphene is more remarkable in electrochemical reactions. Additionally, heteroatoms doping with metal-free materials can obtain unique structure and demonstrate excellent electrocatalytic performance. In this work, we proposed a facile method to prepare bifunctional electrocatalyst which was constructed by nitrogen, sulfur doped graphene (NSG), which demonstrate superior properties with high activity and excellent durability compared with Pt/C and IrO₂ for oxygen reduction (OR) and oxygen evolution (OE) reactions. Accordingly, these phenomena are closely related to the synergistic effect of doping with nitrogen and sulfur by rationally regulating the polarity of carbon in graphene. The current work expands the method towards carbon materials with heteroatom dopants for commercialization in energy-related reactions. Full article

Copper oxide supported on alumina and copper chromite were synthesized, characterized, and subsequently tested for their catalytic activity toward the hydrogenation of octanal. Thereafter, the impact of water addition on the conversion and selectivity of the catalysts were investigated. The fresh catalysts were characterized using X-ray diffraction (XRD), BET surface area and pore volume, SEM, TEM, TGA-DSC, ICP, TPR, and TPD. An initial catalytic testing study was carried out using the catalysts to optimize the temperature and the hydrogen-to-aldehyde ratio—which were found to be 160 °C and 2, respectively—to obtain the best conversion and selectivity to octanol prior to water addition. Water impact studies were carried out under the same conditions. The copper chromite catalyst showed no deactivation or change in octanol selectivity when water was added to the feed. The alumina-supported catalyst showed no change in conversion, but the octanol selectivity improved marginally when water was added. Full article

As natural oligo- and polysaccharides are important biomass resources and exhibit vital biological functions, non-natural oligo- and polysaccharides with a well-defined structure can be expected to act as new functional materials with specific natures and properties. α-Glucan phosphorylase (GP) is one of the enzymes that have been used as catalysts for practical synthesis of oligo- and polysaccharides. By means of weak specificity for the recognition of substrates by GP, non-natural oligo- and polysaccharides has precisely been synthesized. GP-catalyzed enzymatic glycosylations using several analog substrates as glycosyl donors have been carried out to produce oligosaccharides having different monosaccharide residues at the non-reducing end. Glycogen, a highly branched natural polysaccharide, has been used as the polymeric glycosyl acceptor and primer for the GP-catalyzed glycosylation and polymerization to obtain glycogen-based non-natural polysaccharide materials. Under the conditions of removal of inorganic phosphate, thermostable GP-catalyzed enzymatic polymerization of analog monomers occurred to give amylose analog polysaccharides. Full article

The use of diphenyl ether (DE) and its 4-monohalogenated derivatives (4-HDE) as flame retardants, solvents, and substrates in biocide production significantly increases the risk of ecosystem contamination. Their removal is important from the point of view of environmental protection. The aim of this study was to evaluate the degradation processes of DE and 4-HDE by enzymes of the environmental bacterial strains under one-substrate and co-metabolic conditions. The study is focused on the biodegradation of DE and 4-HDE, the enzymatic activity of microbial strains, and the cell surface properties after contact with compounds. The results show that the highest biodegradation (96%) was observed for 4-chlorodiphenyl ether in co-metabolic culture with P. fluorescens B01. Moreover, the activity of 1,2-dioxygenase during degradation of 4-monohalogenated diphenyl ethers was higher than that of 2,3-dioxygenase for each strain tested. The presence of a co-substrate provoked changes in dioxygenase activity, resulting in the increased activity of 1,2-dioxygenase. Moreover, the addition of phenol as a co-substrate allowed for increased biodegradation of the diphenyl ethers and noticeable modification of the cell surface hydrophobicity during the process. All observations within the study performed have led to a deeper understanding of the contaminants’ biodegradation processes catalyzed by environmental bacteria. Full article

The high cost and environmental impact of fossil-based organic carriers represent a critical bottleneck to their use in large-scale industrial processes. The present study demonstrates the applicability of rice husk as inexpensive renewable carrier for the immobilization of enzymes applicable sectors where the covalent anchorage of the protein is a pre-requisite for preventing protein contamination while assuring the recyclability. Rice husk was oxidized and then functionalized with a di-amino spacer. The morphological characterization shed light on the properties that affect the functionalization processes. Lipase B from Candida antarctica (CaLB) and two commercial asparaginases were immobilized covalently achieving higher immobilization yield than previously reported. All enzymes were immobilized also on commercial epoxy methacrylic resins and the CaLB immobilized on rice husk demonstrated a higher efficiency in the solvent-free polycondensation of dimethylitaconate. CaLB on rice husk appears particularly suitable for applications in highly viscous processes because of the unusual combination of its low density and remarkable mechanical robustness. In the case of the two asparaginases, the biocatalyst immobilized on rice husk performed in aqueous solution at least as efficiently as the enzyme immobilized on methacrylic resins, although the rice husk loaded a lower amount of protein. Full article

The stereoselective synthesis of chiral amines is an appealing task nowadays. In this context, biocatalysis plays a crucial role due to the straightforward conversion of prochiral and racemic ketones into enantiopure amines by means of a series of enzyme classes such as amine dehydrogenases, imine reductases, reductive aminases and amine transaminases. In particular, the stereoselective synthesis of 1,5-benzoxathiepin-3-amines have attracted particular attention since they possess remarkable biological profiles; however, their access through biocatalytic methods is unexplored. Amine transaminases are applied herein in the biotransamination of 3,4-dihydro-2H-1,5-benzoxathiepin-3-one, finding suitable enzymes for accessing both target amine enantiomers in high conversion and enantiomeric excess values. Biotransamination experiments have been analysed, trying to optimise the reaction conditions in terms of enzyme loading, temperature and reaction times. Full article

Ceria supported metal catalysts often exhibit high activity in the preferential oxidation (PROX) of CO in H₂-rich stream and doping the ceria support with other metals proves to be rather effective in further enhancing their catalytic performance. Therefore, in this work, a series of ceria materials doped with Mn, Fe and Ni (CeM, where M = Mn, Fe and Ni; M/Ce = 1/8) were synthesized by a modified hydrothermal method; with the doped ceria materials (CeM) as the support, various supported gold catalysts (Au/CeM) were prepared by the colloidal deposition method. The influence of metal dopant on the performance of these ceria materials supported with gold catalysts in CO PROX was then investigated in detail with the help of various characterization measures such as N₂ sorption, XRD, TEM, Raman spectroscopy, H₂-TPR, XPS and XAS. The results indicate that the incorporation of Mn, Fe and Ni metal ions into ceria can remarkably increase the amount of oxygen vacancies in the doped ceria support, which is beneficial for enhancing the reducibility of ceria, the metal-support interaction and the dispersion of gold species. Although the gold catalysts supported on various doped ceria are similar in the size and state of Au nanoparticles, the CO conversions for CO PROX over Au/CeMn, Au/CeFe and Au/CeNi catalysts are 65.6%, 93.0% and 48.2%, respectively, much higher than the value of 33.6% over the undoped Au/CeO₂ catalyst at ambient temperature. For CO PROX over the Au/CeNi catalyst, the conversion of CO remains near 100% at 60–130 °C, with a PROX selectivity to CO₂ of higher than 50%. The excellent performance of Au/CeNi catalyst can be ascribed to its large amount of oxygen vacancies and high reducibility on account of Ni incorporation. The insight shown in this work helps to clarify the doping effect of other metals on the physicochemical properties of ceria, which is then beneficial to building a structure-performance relation for ceria supported gold catalyst as well as developing a better catalyst for removing trace CO in the hydrogen stream and producing high purity hydrogen. Full article

In this present study, we proposed a smart biomineralization method for creating hybrid organic–inorganic nanoflowers using a Co²⁺-dependent enzyme (D-psicose 3-epimerase; DPEase) as the organic component and cobalt phosphate as the inorganic component. The prepared nanoflowers have many separated petals that have a nanometer size. Under optimum conditions (60 °C and pH of 8.5), the nanoflower can display its maximum activity (36.2 U/mg), which is about 7.2-fold higher than free DPEase. Furthermore, the immobilized DPEase presents enhanced pH and thermal stabilities. The DPEase-nanoflower maintained about 90% of its activity after six reaction cycles, highlighting its excellent reusability. Full article

In this work, a heterogeneous catalytic system consisting of [HO₂CMMIm]Cl and ZrOCl₂ in isopropanol is demonstrated to be effective for 5-hydroxymethylfurfural (HMF) synthesis with glucose as the feedstock. Various reaction conditions for HMF synthesis by glucose dehydration were investigated systematically. Under optimized reaction conditions, as high as 43 mol% HMF yield could be achieved. Increasing the water content to a level below 3.17% led to the production of HMF with a higher yield, while a lower HMF yield was observed when the water content was increased above 3.17%. In addition, the data also showed that ZrOCl₂ could not only effectively convert glucose into intermediate species (which were not fructose, in contrast to the literature) but also catalyze the intermediate species’ in situ dehydration into HMF. [HO₂CMMIm]Cl was used to catalyze the intermediate species’ in situ conversion to HMF. The kinetics data showed that a temperature increase accelerated the intermediate species’ dehydration reaction rate. The reaction of glucose dehydration was a strong endothermal reaction. Full article

Volatile Organic Compounds (VOCs) are within the main industrial air pollutants whose release into the atmosphere is harmful to the ecosystem and human health. Gas-phase photocatalytic degradation of ethylbenzene, an aromatic VOC emitted from various sources, has been investigated in this study using TiO₂ nanoparticle-coated glass beads in an annular photoreactor. To use visible light irradiation, TiO₂ nanoparticles were doped by nitrogen using urea. The results showed that nitrogen doping significantly increased the removal efficiency of ethylbenzene under visible light irradiation compared with the pure TiO₂, so that the removal efficiencies between 75–100% could be yielded for the initial ethylbenzene concentrations up to 0.13 g/m³ under visible light which could be useful for improving indoor air quality. The UV irradiated reactor needed less residence time and much higher removal efficiencies could be yielded at high initial concentrations. When the residence time under UV irradiation was one third of the same under visible light, the removal efficiency was more than 80% for the inlet concentrations up to 0.6 g/m³, whereas the removal efficiency under visible light was about 25% at this inlet concentration. Langmuir-Hinshelwood kinetic model could be well fitted to the photocatalytic reaction in both irradiation systems. Full article

The Pt-Bi (Bi₂O₃)/GNs (PVP) composite was synthesized using aqueous solution synthesis and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and Raman spectroscopy. It was found that the water-soluble polyvinyl pyrrolidone (PVP) helped to tune the particles’ morphology, resulting in a uniform distribution of Pt-Bi nanoclusters on the surface of graphene. Cyclic voltammetry, chronoamperometry and linear scanning voltammetry (LSV) were used to study the electrocatalytic properties towards a methanol oxidation reaction (MOR) and an oxygen reduction reaction (ORR). The results show that Pt-Bi (Bi₂O₃)/GNs (PVP) exhibits superior bifunctional electrocatalytic properties for both MOR and ORR, mainly due to the introduction of oxophilic Bi species and the better dispersion of the Pt-Bi nanoclusters. In particular, the electro-photo catalysis for both MOR and ORR occurred under simulated sunlight irradiation due to the existence of photo-responsive Bi species, which is helpful for converting solar energy into electric energy during a traditional electrocatalytic process. Full article

Oxidative cleavage of fatty acids and fatty acid derivatives is a practical way to obtain bifunctional molecules that can be used in polycondensation reactions. Diacids, hydroxyacids, and amino acids can then be used to produce polyesters or polyamides and also a large range of other products, such as lubricants and plasticizers. Ozonolysis has long been the sole industrial process for oxidative cleavage, but recently, routes using hydrogen peroxide as a clean oxidant have regained interest. Hydrogen peroxide is easier to use, but the kinetics of the catalyzed reactions are still slow. Although several catalytic systems have been described in the literature, tungsten-based catalysts are still the preferred choices. Different catalysts can trigger different mechanisms, such as a radical mechanism instead of a catalytic reaction. In addition, some side products and co-products often disregarded in the literature, such as shorted cleavage products, indicate the presence of side reactions that affect the quality of the final products. The oxidative cleavages in continuous and batch processes have significant differences, which are discussed with an illustration of our understanding of the process used by Matrica S.p.A. Full article

Plasmonic nanostructures can be employed for performing photocatalytic reactions with visible-light illumination involving two different possible mechanisms, namely, the near-field enhancement and/or direct hot-electron transfer to the conduction band of an active catalyst. In this study, we demonstrate the significant contribution of a graphene interface layer present between plasmonic nanoparticles and active catalysts (Pd nanodots) in enhancing the photocatalytic efficiency of Pd nanodots through an accelerated electron transfer process. The well-defined Pd-nanodot-modified gold nanoparticles with or without a graphene interface layer were prepared using a wet-chemical synthetic method. The role of the graphene interface was investigated by performing wavelength-dependent reduction studies using potassium hexacyanoferrate (III) in the presence of Pd-nanodot-modified cysteamine-modified AuNPs (Pd-cys-AuNPs), Pd-nanodot-modified graphene oxide (GO)-coated AuNPs (Pd-GO-AuNPs), and Pd-nanodot-modified reduced GO (rGO)-coated AuNPs (Pd-rGO-AuNPs). The fastest rate for the reduction of Fe³⁺ to Fe²⁺ was obtained with Pd-rGO-AuNPs because of the fast electron transfer achieved in the presence of the reduced graphene oxide layer. The highest catalytic activity for the visible-light induced C-C coupling reaction was obtained with Pd-rGO-AuNPs, indicating the role of the graphene interface layer. These results indicate that the design and use of engineered interfaces are of importance to achieve enhanced catalytic activity with plasmonic hybrid nanomaterials. Full article

Here, we demonstrate the enhanced water-splitting performance (I = 10 mA/cm², Tafel slope = 60 mV/dec, onset potential = −80 mV) of atmospheric air plasma treated (AAPT) SnS thin films by the hydrogen evolution reaction (HER). The as prepared SnS films were subjected to Atmospheric Air Plasma Treatment (AAPT) which leads to formation of additional phases of Sn and SnO₂ at plasma powers of 150 W and 250 W, respectively. The AAPT treatment at 150 W leads to the evaporation of the S atoms as SO₂ generates a number of S-vacancies and Sn active edge sites over the surface of the SnS thin film. S-vacancies also create Sn active edge sites, surface p-type pinning that tunes the suitable band positions, and a hydrophilic surface which is beneficial for hydrogen adsorption/desorption. At high plasma power (250 W), the surface of the SnS films becomes oxidized and degrades the HER performance. These results demonstrate that AAPT (150 W) is capable of improving the HER performance of SnS thin films and our results indicate that SnS thin films can work as efficient electrocatalysts for HER. Full article

In this work, hierarchical nanostructured Pr₆O₁₁ thin-films of brain-like morphology were successfully prepared by electrostatic spray deposition (ESD) on glassy-carbon substrates. These surfaces were used as working electrodes in the rotating disk electrode (RDE) setup and characterized in alkaline electrolyte (0.1 M NaOH at 25 ± 2 °C) for the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR) for their potential application in alkaline electrolyzers or in alkaline fuel cells. The electrochemical performances of these electrodes were investigated as a function of their crystallized state (amorphous versus crystalline). Although none of the materials display spectacular HER and OER activity, the results show interesting performances of the crystallized sample towards the ORR with regards to this class of non-Pt group metal (non-PGM) electrocatalysts, the activity being, however, still far from a benchmark Pt/C electrocatalyst. Full article

Enzymes are efficient biocatalysts providing an important tool in many industrial biocatalytic processes. Currently, the immobilized enzymes prepared by the cross-linked enzyme aggregates (CLEAs) have drawn much attention due to their simple preparation and high catalytic efficiency. Combined cross-linked enzyme aggregates (combi-CLEAs) including multiple enzymes have significant advantages for practical applications. In this review, the conditions or factors for the preparation of combi-CLEAs such as the proportion of enzymes, the type of cross-linker, and coupling temperature were discussed based on the reaction mechanism. The recent applications of combi-CLEAs were also reviewed. Full article

Indole is the most frequently found heterocyclic core structures in pharmaceuticals, natural products, agrochemicals, dyes and fragrances. For about 150 years, chemists were absorbed in finding new and easier synthetic strategies to build this nucleus. Many books and reviews have been written, but the number of new syntheses that appear in the literature, make necessary continuous updates. This reviews aims to give a comprehensive overview on indole synthesis catalyzed by transition metals appeared in the literature in the years 2016 and 2017. Full article