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Catalysts, Volume 12, Issue 12 (December 2022) – 188 articles

Cover Story (view full-size image): With the increase in biodiesel production in recent years, excess production of glycerol is a reality. Glycerol is now a platform chemical that can be transformed into various chemical intermediates, including prodrugs of NSAIDs such as ibuprofen, reducing the adverse effects of their chronic administration. Their production by mild esterification with lipases is a possibility, while the development of continuous or flow processes based on multiphase systems in the pharma industry is key for process intensification and product quality. For the first time, we show that the appropriate selection of cosolvents such as glycerol, toluene, and water and of process conditions leads to high stability and activity of the commercial preparation Novozym®435, an immobilised biocatalyst based on lipase B from Candida antarctica. View this paper
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Article
Preparation of CuS/PbS/ZnO Heterojunction Photocatalyst for Application in Hydrogen Production
Catalysts 2022, 12(12), 1677; https://doi.org/10.3390/catal12121677 - 19 Dec 2022
Viewed by 550
Abstract
A hexagonal wurtzite ZnO photocatalyst was prepared via a precipitation method. CuS nanoparticles (NPs) and PbS quantum dots (QDs) were loaded onto ZnO via a hydrothermal method to obtain a CuS/PbS/ZnO heterojunction photocatalyst. The CuS/PbS/ZnO photocatalyst obtained via the abovementioned method has significant [...] Read more.
A hexagonal wurtzite ZnO photocatalyst was prepared via a precipitation method. CuS nanoparticles (NPs) and PbS quantum dots (QDs) were loaded onto ZnO via a hydrothermal method to obtain a CuS/PbS/ZnO heterojunction photocatalyst. The CuS/PbS/ZnO photocatalyst obtained via the abovementioned method has significant absorption capabilities in the ultraviolet to near-infrared spectral regions, and effectively reduced the recombination of electron–hole pairs during a photocatalytic reaction. Electron microscope images showed that in the CuS/PbS/ZnO photocatalyst prepared at 130 °C, the particle size of the PbS QDs was approximately 5.5–5.7 nm, and the bandgap determined from the Tauc plot was 0.84 eV; this catalyst demonstrated the best water splitting effect. Furthermore, after adding a 0.25 M mixed solution of Na2S and Na2SO3 as the sacrificial reagent in photocatalysis for 5 h, the hydrogen production efficiency from water splitting reached 6654 μmol g−1 h−1. Full article
(This article belongs to the Special Issue Structured Semiconductors in Photocatalysis)
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Article
Integrated Adsorption-Photocatalytic Decontamination of Oxytetracycline from Wastewater Using S-Doped TiO2/WS2/Calcium Alginate Beads
Catalysts 2022, 12(12), 1676; https://doi.org/10.3390/catal12121676 - 19 Dec 2022
Viewed by 478
Abstract
Integrated wastewater treatment processes are needed due to the inefficient removal of emerging pharmaceuticals by single methods. Herein, an adsorbent-photocatalyst integrated material was fabricated by coupling calcium alginate with sulfur-doped TiO2/tungsten disulfide (S-TiO2/WS2/alginate beads) for the removal [...] Read more.
Integrated wastewater treatment processes are needed due to the inefficient removal of emerging pharmaceuticals by single methods. Herein, an adsorbent-photocatalyst integrated material was fabricated by coupling calcium alginate with sulfur-doped TiO2/tungsten disulfide (S-TiO2/WS2/alginate beads) for the removal of oxytetracycline (OTC) from aqueous solution by an integrated adsorption-photocatalysis process. The semiconductor S-TiO2/WS2 hybrid photocatalyst was synthesized with a hydrothermal method, while the integrated adsorbent-photocatalyst S-TiO2/WS2/alginate beads were synthesized by blending S-TiO2/WS2 with sodium alginate using calcium chloride as a precipitating agent. The physicochemical characteristics of S-TiO2/WS2/alginate beads were analyzed using X-ray diffraction , scanning electron microscopy, elemental mapping, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. The integrated adsorption-photocatalysis process showed enhanced removal from 92.5 to 72%, with a rise in the OTC concentration from 10 to 75 mg/L respectively. The results demonstrated that the adsorption of OTC onto S-TiO2/WS2/alginate beads followed the Elovich kinetic model and Redlich–Peterson isotherm models. The formations of H-bonds, cation bridge bonding, and n-π electron donor-acceptor forces were involved in the adsorption of OCT onto S-TiO2/WS2/alginate beads. In the integrated adsorption-photocatalysis, surface-adsorbed OTC molecules were readily decomposed by the photogenerated active radical species (h⁺, O2•−, and HO). The persulfate addition to the OTC solution further increased the photocatalysis efficacy due to the formation of additional oxidizing species (SO4⁻, SO4⁻). Moreover, S-TiO2/WS2/alginate beads showed favorable efficiency and sustainability in OTC removal, approaching 78.6% after five cycles. This integrated adsorption-photocatalysis process offered significant insight into improving efficiency and reusability in water treatment. Full article
(This article belongs to the Special Issue Nanomaterials-Based Catalysts for Degradation of Pollutants)
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Article
Electrochemical Detection of Sulfite by Electroreduction Using a Carbon Paste Electrode Binder with N-octylpyridinium Hexafluorophosphate Ionic Liquid
Catalysts 2022, 12(12), 1675; https://doi.org/10.3390/catal12121675 - 19 Dec 2022
Viewed by 412
Abstract
Sulfite is a widely used additive in food and beverages, and its maximum content is limited by food regulations. For this reason, determining the sulfite concentration using fast, low-cost techniques is a current challenge. This work describes the behavior of a sensor based [...] Read more.
Sulfite is a widely used additive in food and beverages, and its maximum content is limited by food regulations. For this reason, determining the sulfite concentration using fast, low-cost techniques is a current challenge. This work describes the behavior of a sensor based on an electrode formed by carbon nanotubes an ionic liquid as binder, which by electrochemical reduction, allows detecting sulfite with a detection limit of 1.6 ± 0.05 mmol L−1 and presents adequate sensitivity. The advantage of detecting sulfite by reduction and not by oxidation is that the presence of antioxidants such as ascorbic acid does not affect the measurement. The electrode shown here is low-cost and easy to manufacture, robust, and stable. Full article
(This article belongs to the Special Issue Electrocatalysts for Oxidation-Reduction Reactions)
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Review
Catalytic Efficiency of Primary α-Amino Amides as Multifunctional Organocatalysts in Recent Asymmetric Organic Transformations
Catalysts 2022, 12(12), 1674; https://doi.org/10.3390/catal12121674 - 19 Dec 2022
Viewed by 465
Abstract
Chiral primary α-amino amides, consisting of an adjacent enamine bonding site (Bronsted base site), a hydrogen bonding site (Bronsted acid site), and flexible bulky substituent groups to modify the steric factor, are proving to be extremely valuable bifunctional organocatalysts for a wide range [...] Read more.
Chiral primary α-amino amides, consisting of an adjacent enamine bonding site (Bronsted base site), a hydrogen bonding site (Bronsted acid site), and flexible bulky substituent groups to modify the steric factor, are proving to be extremely valuable bifunctional organocatalysts for a wide range of asymmetric organic transformations. Primary α-amino amides are less expensive alternatives to other primary amino organocatalysts, such as chiral diamines and cinchona-alkaloid-derived primary amines, as they are easy to synthesize, air-stable, and allow for the incorporation of a variety of functional groups. In recent years, we have demonstrated the catalytic use of simple primary α-amino amides and their derivatives as organocatalysts for the aldol reaction, Strecker reaction, Michael tandem reaction, allylation of aldehydes, reduction of N-Aryl mines, opening of epoxides, hydrosilylation, asymmetric hydrogen transfer, and N-specific nitrosobenzene reaction with aldehydes. Full article
(This article belongs to the Special Issue Advances in Asymmetric Organocatalytic Reactions)
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Article
Lipozyme® TL IM Biocatalyst for Castor Oil FAME and Triacetin Production by Interesterification: Activity, Stability, and Kinetics
Catalysts 2022, 12(12), 1673; https://doi.org/10.3390/catal12121673 - 19 Dec 2022
Viewed by 551
Abstract
Global climate change and present geopolitical tensions call for novel, renewable, and, ideally, sustainable resources and processes that, in the end, will be integrated in the natural cycles of carbon and water, progressively replacing non-renewable feedstocks. In this context, the production of biofuels [...] Read more.
Global climate change and present geopolitical tensions call for novel, renewable, and, ideally, sustainable resources and processes that, in the end, will be integrated in the natural cycles of carbon and water, progressively replacing non-renewable feedstocks. In this context, the production of biofuels and, in consequence, of biodiesel plays a notable role. This work is focused on the production of fatty acid methyl esters (FAME) from castor oil, an abundant non-edible oil, using a sustainable technology approach based on industrial lipases and methyl acetate as a methylating reagent to reduce biocatalyst inactivation. We have selected a stable industrial enzyme preparation to determine its suitability for FAME production: Lipozyme® TL IM (an inexpensive lipase from Thermomyces lanuginosus immobilized by agglomeration in silica gel). Several operational variables affecting the enzyme activity have been studied: methanol excess (6:1 to 13:1), temperature (from 40 to 60 °C), and enzyme concentration (10 and 30% w/w). At all temperatures and reagent ratios, we have also tested the enzyme stability for six cycles, showing its low to negligible inactivation under operational conditions. Finally, a novel multivariable kinetic model has been proposed and fitted to experimental data obtained in a wide experimental range for the first time, showing that direct and reverse in-series reactions are present. We have estimated the values of the kinetic constants and their standard errors, and goodness-of-fit parameters, observing that the kinetic model fitted very reasonably to all retrieved experimental data at the same time. Full article
(This article belongs to the Special Issue Catalysts for Biofuel and Bioenergy Production)
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Article
Insight into the Effect of Anionic–Anionic Co-Doping on BaTiO3 for Visible Light Photocatalytic Water Splitting: A First-Principles Hybrid Computational Study
Catalysts 2022, 12(12), 1672; https://doi.org/10.3390/catal12121672 - 19 Dec 2022
Viewed by 701
Abstract
In this research, we thoroughly studied the electronic properties and optical absorption characteristics with double-hole coupling of anions–anion combinations for designing effective photocatalysts for water redox using first-principles methods within the hybrid Heyd–Scuseria–Ernzerhof (HSE06) exchange–correlation formalisms. The findings reveal that the values of [...] Read more.
In this research, we thoroughly studied the electronic properties and optical absorption characteristics with double-hole coupling of anions–anion combinations for designing effective photocatalysts for water redox using first-principles methods within the hybrid Heyd–Scuseria–Ernzerhof (HSE06) exchange–correlation formalisms. The findings reveal that the values of formation energy of both the anion mono- and co-doped configurations increase monotonically as the chemical potential of oxygen decreases. The N–N co-doped BaTiO3 exhibits a more favorable formation energy under an O-poor condition compared with other configurations, indicating that N and N pairs are more likely to be synthesized successfully. Interestingly, all the co-doping configurations give a band gap reduction with suitable position for oxygen production and hydrogen evolution. The obtained results demonstrate that all the co-doped systems constitute a promising candidate for photocatalytic water-splitting reactions. Furthermore, the enhanced ability of the anionic-anionic co-doped BaTiO3 to absorb visible light and the positions of band edges that closely match the oxidation-reduction potentials of water suggest that these configurations are viable photocatalysts for visible-light water splitting. Therefore, the wide-band gap semiconductor band structures can be tuned by double-hole doping through anionic combinations, and high-efficiency catalysts for water splitting using solar energy can be created as a result. Full article
(This article belongs to the Special Issue Catalytic Processes for Water and Wastewater Treatment)
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Article
Unsupported Ni—Mo—W Hydrotreating Catalyst: Influence of the Atomic Ratio of Active Metals on the HDS and HDN Activity
Catalysts 2022, 12(12), 1671; https://doi.org/10.3390/catal12121671 - 19 Dec 2022
Viewed by 520
Abstract
Hydrotreating is one of the largest processes used in a refinery to improve the quality of oil products. The great demand of the present is to develop more active catalysts which could improve the energy efficiency of the process when it is necessary [...] Read more.
Hydrotreating is one of the largest processes used in a refinery to improve the quality of oil products. The great demand of the present is to develop more active catalysts which could improve the energy efficiency of the process when it is necessary for heavier feedstock to be processed. Unsupported catalysts could solve this problem, because they contain the greatest amount of sulfide active sites, which significantly increase catalysts’ activity. Unfortunately, most of the information on the preparation and properties of unsupported catalysts is devoted to powder systems, while industrial plants require granular catalysts. Therefore, the present work describes a method for the preparation of granular Ni—Mo—W unsupported hydrotreating catalysts and studies the influence of the Ni/Mo/W atomic ratio on their properties. Catalysts have been prepared by plasticizing Ni—Mo—W precursor with aluminum hydroxide followed by granulation and drying stages. Ni—Mo—W precursor and granular catalysts were studied by X-ray diffraction (XRD), nitrogen adsorption–desorption method, high-resolution transmission electron microscopy (HRTEM), and thermal analysis. Granular catalysts were sulfided through a liquid-phase sulfidation procedure and tested in hydrotreating of straight-run vacuum gasoil. It was shown that the Ni/Mo/W atomic ratio influenced the formation and composition of active compounds and had almost no influence on the textural properties of catalysts. The best hydrodesulfurization (HDS) activity was obtained for the catalyst with Ni/Mo/W ratio—1/0.15/0.85, while hydrodenitrogenation (HDN) activity of the catalysts is very similar. Full article
(This article belongs to the Special Issue Ni-Based Catalysts: Synthesis and Applications)
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Article
Sulfur-Resistant CeO2-Supported Pt Catalyst for Waste-to-Hydrogen: Effect of Catalyst Synthesis Method
Catalysts 2022, 12(12), 1670; https://doi.org/10.3390/catal12121670 - 19 Dec 2022
Viewed by 442
Abstract
To improve the sulfur tolerance of CeO2-supported Pt catalysts for water gas shift (WGS) using waste-derived synthesis gas, we investigated the effect of synthesis methods on the physicochemical properties of the catalysts. The Pt catalysts using CeO2 as a support [...] Read more.
To improve the sulfur tolerance of CeO2-supported Pt catalysts for water gas shift (WGS) using waste-derived synthesis gas, we investigated the effect of synthesis methods on the physicochemical properties of the catalysts. The Pt catalysts using CeO2 as a support were synthesized in various pathways (i.e., incipient wetness impregnation, sol-gel, hydrothermal, and co-precipitation methods). The prepared samples were then evaluated in the WGS reaction with 500 ppm H2S. Among the prepared catalysts, the Pt-based catalyst prepared by incipient wetness impregnation showed the highest catalytic activity and sulfur tolerance due to the standout factors such as a high oxygen-storage capacity and active metal dispersion. The active metal dispersion and oxygen-storage capacity of the catalyst showed a correlation with the catalytic performance and the sulfur tolerance. Full article
(This article belongs to the Special Issue Nanocatalysts for Carbon Upcycling)
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Article
Single Metal Atoms Embedded in the Surface of Pt Nanocatalysts: The Effect of Temperature and Hydrogen Pressure
Catalysts 2022, 12(12), 1669; https://doi.org/10.3390/catal12121669 - 19 Dec 2022
Viewed by 518
Abstract
Embedding energetically stable single metal atoms in the surface of Pt nanocatalysts exposed to varied temperature (T) and hydrogen pressure (P) could open up new possibilities in selective and dynamical engineering of alloyed Pt catalysts, particularly interesting for hydrogenation reactions. In this work, [...] Read more.
Embedding energetically stable single metal atoms in the surface of Pt nanocatalysts exposed to varied temperature (T) and hydrogen pressure (P) could open up new possibilities in selective and dynamical engineering of alloyed Pt catalysts, particularly interesting for hydrogenation reactions. In this work, an environmental segregation energy model is developed to predict the stability and the surface composition evolution of 24 Metal M-promoted Pt surfaces (with M: Cu, Ag, Au, Ni, Pd, Co, Rh and Ir) under varied T and P. Counterintuitive to expectations, the results show that the more reactive alloy component (i.e., the one forming the strongest chemical bond with the hydrogen) is not the one that segregates to the surface. Moreover, using DFT-based Multi-Scaled Reconstruction (MSR) method and by extrapolation of M-promoted Pt nanoparticles (NPs), the shape dynamics of M-Pt are investigated under the same ranges of T and P. The results show that under low hydrogen pressure and high temperature ranges, Ag and Au—single atoms (and Cu to a less extent) are energetically stable on the surface of truncated octahedral and/or cuboctahedral shaped NPs. This indicated that coinage single-atoms might be used to tune the catalytic properties of Pt surface under hydrogen media. In contrast, bulk stability within wide range of temperature and pressure is predicted for all other M-single atoms, which might act as bulk promoters. This work provides insightful guides and understandings of M-promoted Pt NPs by predicting both the evolution of the shape and the surface compositions under reaction gas condition. Full article
(This article belongs to the Special Issue Reactivity and Structural Dynamics of Catalysts)
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Article
Heterojunction Design between WSe2 Nanosheets and TiO2 for Efficient Photocatalytic Hydrogen Generation
Catalysts 2022, 12(12), 1668; https://doi.org/10.3390/catal12121668 - 19 Dec 2022
Viewed by 689
Abstract
Design and fabrication of efficient and stable photocatalysts are critically required for practical applications of solar water splitting. Herein, a series of WSe2/TiO2 nanocomposites were constructed through a facile mechanical grinding method, and all of the nanocomposites exhibited boosted photocatalytic [...] Read more.
Design and fabrication of efficient and stable photocatalysts are critically required for practical applications of solar water splitting. Herein, a series of WSe2/TiO2 nanocomposites were constructed through a facile mechanical grinding method, and all of the nanocomposites exhibited boosted photocatalytic hydrogen evolution. It was discovered that the enhanced photocatalytic performance was attributed to the efficient electron transfer from TiO2 to WSe2 and the abundant active sites provided by WSe2 nanosheets. Moreover, the intimate heterojunction between WSe2 nanosheets and TiO2 favors the interfacial charge separation. As a result, a highest hydrogen evolution rate of 2.28 mmol/g·h, 114 times higher than pristine TiO2, was obtained when the weight ratio of WSe2/(WSe2 + TiO2) was adjusted to be 20%. The designed WSe2/TiO2 heterojunctions can be regarded as a promising photocatalysts for high-throughput hydrogen production. Full article
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Article
Study on the Formaldehyde Oxidation Reaction of Acid-Treated Manganese Dioxide Nanorod Catalysts
Catalysts 2022, 12(12), 1667; https://doi.org/10.3390/catal12121667 - 18 Dec 2022
Viewed by 507
Abstract
Formaldehyde is an important downstream chemical of syngas. Furniture and household products synthesized from formaldehyde will slowly decompose and release formaldehyde again during use, which seriously affects indoor air quality. In order to solve the indoor formaldehyde pollution problem, this paper took the [...] Read more.
Formaldehyde is an important downstream chemical of syngas. Furniture and household products synthesized from formaldehyde will slowly decompose and release formaldehyde again during use, which seriously affects indoor air quality. In order to solve the indoor formaldehyde pollution problem, this paper took the catalytic oxidation of formaldehyde as the research object; prepared a series of low-cost, acid-treated manganese dioxide nanorod catalysts; and investigated the effect of the acid-treatment conditions on the catalysts’ activity. It was found that the MnNR-0.3ac-6h catalyst with 0.3 mol/L sulfuric acid for 6 h had the best activity. The conversion rate of formaldehyde reached 98% at 150 °C and 90% at 25 °C at room temperature. During the reaction time of 144 h, the conversion rate of formaldehyde was about 90%, and the catalyst maintained a high activity. It was found that acid treatment could increase the number of oxygen vacancies on the surface of the catalysts and promote the production of reactive oxygen species. The amount of surface reactive oxygen species of the MnNR-0.3ac-6h catalyst was about 13% higher than that of the catalyst without acid treatment. Full article
(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)
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Article
Catalytic Degradation of Toluene over MnO2/LaMnO3: Effect of Phase Type of MnO2 on Activity
Catalysts 2022, 12(12), 1666; https://doi.org/10.3390/catal12121666 - 18 Dec 2022
Viewed by 468
Abstract
Series of α, β, γ, δ type MnO2 supported on LaMnO3 perovskite was developed by a one-pot synthesis route. Compared with α-MnO2, β-MnO2, γ-MnO2, δ-MnO2 and LaMnO3 oxides, all MnO2/LaMnO3 [...] Read more.
Series of α, β, γ, δ type MnO2 supported on LaMnO3 perovskite was developed by a one-pot synthesis route. Compared with α-MnO2, β-MnO2, γ-MnO2, δ-MnO2 and LaMnO3 oxides, all MnO2/LaMnO3 showed promotional catalytic performance for toluene degradation. Among them, α-MnO2/LaMnO3 holds the best active and mineralization efficiency. By the analysis of N2 adsorption-desorption, XPS and H2-TPR, it can be inferred that the improved activity should be ascribed to the higher proportion of lattice oxygen, better low-temperature reducibility and larger specific surface area. Besides, the byproducts from the low-temperature reaction of toluene oxidation were detected by a TD/GC-MS, confirming the presence of the intermediates. Combined with the in-situ DRIFTS, the catalytic degradation path of toluene oxidation has also been discussed in depth. Full article
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Review
Advances in Catalytic C–F Bond Activation and Transformation of Aromatic Fluorides
Catalysts 2022, 12(12), 1665; https://doi.org/10.3390/catal12121665 - 18 Dec 2022
Viewed by 479
Abstract
The activation and transformation of C–F bonds in fluoro-aromatics is a highly desirable process in organic chemistry. It provides synthetic methods/protocols for the generation of organic compounds possessing single or multiple C–F bonds, and effective catalytic systems for further study of the activation [...] Read more.
The activation and transformation of C–F bonds in fluoro-aromatics is a highly desirable process in organic chemistry. It provides synthetic methods/protocols for the generation of organic compounds possessing single or multiple C–F bonds, and effective catalytic systems for further study of the activation mode of inert chemical bonds. Due to the high polarity of the C–F bond and it having the highest bond energy in organics, C–F activation often faces considerable academic challenges. In this mini-review, the important research achievements in the activation and transformation of aromatic C–F bond, catalyzed by transition metal and metal-free systems, are presented. Full article
(This article belongs to the Topic Catalysis: Homogeneous and Heterogeneous)
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Review
Novel Challenges on the Catalytic Synthesis of 5-Hydroxymethylfurfural (HMF) from Real Feedstocks
Catalysts 2022, 12(12), 1664; https://doi.org/10.3390/catal12121664 - 18 Dec 2022
Viewed by 541
Abstract
The depletion of fossil resources makes the transition towards renewable ones more urgent. For this purpose, the synthesis of strategic platform-chemicals, such as 5-hydroxymethylfurfural (HMF), represents a fundamental challenge for the development of a feasible bio-refinery. HMF perfectly deals with this necessity, because [...] Read more.
The depletion of fossil resources makes the transition towards renewable ones more urgent. For this purpose, the synthesis of strategic platform-chemicals, such as 5-hydroxymethylfurfural (HMF), represents a fundamental challenge for the development of a feasible bio-refinery. HMF perfectly deals with this necessity, because it can be obtained from the hexose fraction of biomass. Thanks to its high reactivity, it can be exploited for the synthesis of renewable monomers, solvents, and bio-fuels. Sustainable HMF synthesis requires the use of waste biomasses, rather than model compounds such as monosaccharides or polysaccharides, making its production more economically advantageous from an industrial perspective. However, the production of HMF from real feedstocks generally suffers from scarce selectivity, due to their complex chemical composition and HMF instability. On this basis, different strategies have been adopted to maximize the HMF yield. Under this perspective, the properties of the catalytic system, as well as the choice of a suitable solvent and the addition of an eventual pretreatment of the biomass, represent key aspects of the optimization of HMF synthesis. On this basis, the present review summarizes and critically discusses the most recent and attractive strategies for HMF production from real feedstocks, focusing on the smartest catalytic systems and the overall sustainability of the adopted reaction conditions. Full article
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Article
Photocatalytic Degradation of Ciprofloxacin by UV Light Using N-Doped TiO2 in Suspension and Coated Forms
Catalysts 2022, 12(12), 1663; https://doi.org/10.3390/catal12121663 - 18 Dec 2022
Viewed by 518
Abstract
The presence of organic compounds such as ciprofloxacin in untreated pharmaceutical wastewater often poses a serious health risk to human and aquatic life when discharged into water bodies. One of the most effective means of removing ciprofloxacin from wastewater is photocatalytic degradation. However, [...] Read more.
The presence of organic compounds such as ciprofloxacin in untreated pharmaceutical wastewater often poses a serious health risk to human and aquatic life when discharged into water bodies. One of the most effective means of removing ciprofloxacin from wastewater is photocatalytic degradation. However, the synthesis of an effective photocatalyst that can degrade the organic pollutant in the wastewater is often a challenge. Hence, this study focuses on the synthesis and application of nitrogen-doped TiO2 (N-TiO2) in suspension and coated forms for the photocatalytic degradation of ciprofloxacin in wastewater by applying UV-light irradiation. The nitrogen-doped TiO2 photocatalyst was prepared by a co-precipitation process and characterized using energy-dispersive X-ray spectroscopy, scanning electron microscopy, and Fourier-transform infrared spectroscopy. The effects of the initial concentration of the ciprofloxacin (6, 12, 18, or 30 ppm), pH (3, 5, 7, or 9), and flow rate (0.4, 0.8, 0.95, or 1.5 L/min) on the degradation of the ciprofloxacin over the N-TiO2 were investigated. The results showed that the removal efficiency of ciprofloxacin was enhanced by increasing the initial ciprofloxacin concentration, while it was decreased with the increase in the feed flow rate. The best operating conditions were obtained using an initial ciprofloxacin concentration of 30 ppm, pH of 5, and feed flow rate of 0.4 L/min. Under these operating conditions, removal efficiencies of 87.87% and 93.6% were obtained for net TiO2 and N-TiO2 of 5 wt% in suspension form, respectively, while 94.5% ciprofloxacin removal efficiency was obtained using coated 5 wt% N-TiO2 after 2 h of photocatalytic degradation. Based on the response surface optimization strategy, a quadratic model was suggested to obtain mathematical expressions to predict the ciprofloxacin removal efficiency under various studied operational parameters. Full article
(This article belongs to the Special Issue Advances in Photocatalytic Wastewater Purification II)
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Article
Influence of Butanol Isomerization on Photothermal Hydrogen Production over [email protected]2 Core-Shell Nanoparticles
Catalysts 2022, 12(12), 1662; https://doi.org/10.3390/catal12121662 - 17 Dec 2022
Viewed by 487
Abstract
In this work, we reported for the first time the effect of butanol isomerization on the photothermal production of hydrogen in the presence of a noble, metal-free [email protected]2 core-shell photocatalyst. The experiments were performed in aqueous solutions of 1-BuOH, 2-BuOH, and t-BuOH [...] Read more.
In this work, we reported for the first time the effect of butanol isomerization on the photothermal production of hydrogen in the presence of a noble, metal-free [email protected]2 core-shell photocatalyst. The experiments were performed in aqueous solutions of 1-BuOH, 2-BuOH, and t-BuOH under Xe lamp irradiation (vis/NIR: 8.4 W, UV: 0.6 W) at 35–69 °C. The increase in temperature significantly enhanced H2 formation, indicating a strong photothermal effect in the studied systems. However, in dark conditions, H2 emission was not observed even at elevated temperatures, which clearly points out the photonic origin of H2 photothermal formation. The rate of H2 production followed the order of 1-BuOH >> 2-BuOH > t-BuOH in the entire range of studied temperatures. In the systems with 1-BuOH and 2-BuOH, hydrogen was the only gaseous product measured online in the outlet carrier argon using mass spectrometry. By contrast, a mixture of H2, CH4, and C2H6 was detected for t-BuOH, indicating a C–C bond scission with this isomer during photocatalytic degradation. The apparent activation energies, Ea, with 1-BuOH/2-BuOH isomers (20–21 kJ·mol−1) was found to be larger than for t-BuOH (13 kJ·mol−1). The significant difference in thermal response for 1-BuOH/2-BuOH and t-BuOH isomers was ascribed to the difference in the photocatalytic mechanisms of these species. The photothermal effect with 1-BuOH/2-BuOH isomers can be explained by the thermally induced transfer of photogenerated, shallowly trapped electron holes to highly reactive free holes at the surface of TiO2 and the further hole-mediated cleavage of the O-H bond. In the system with t-BuOH, another mechanism could also contribute to the overall process through hydrogen abstraction from the C–H bond by an intermediate OH radical, leading to CH3 group ejection. Formation of OH radicals during light irradiation of [email protected]2 nanoparticle suspension in water has been confirmed using terephthalate dosimetry. This analysis also revealed a positive temperature response of OH radical formation. Full article
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Article
Limestone Calcination Kinetics in Microfluidized Bed Thermogravimetric Analysis (MFB-TGA) for Calcium Looping
Catalysts 2022, 12(12), 1661; https://doi.org/10.3390/catal12121661 - 17 Dec 2022
Viewed by 506
Abstract
Limestone calcination is an important part of calcium looping (CaL) technology and is critical to the design and operation optimization of fluidized bed reactors. However, obtaining a method of measuring the fast calcination kinetics in a fluidizing environment with isothermal conditions is still [...] Read more.
Limestone calcination is an important part of calcium looping (CaL) technology and is critical to the design and operation optimization of fluidized bed reactors. However, obtaining a method of measuring the fast calcination kinetics in a fluidizing environment with isothermal conditions is still a challenge in the field of calcium looping. We address this challenge in this work and develop a new method of obtaining limestone calcination kinetics by injecting limestone particles into the hot fluidizing sands in a microfluidized bed thermogravimetric analysis (MFB-TGA) with a mass measurement resolution of 1 mg. The calcination characteristics of limestone are investigated at different particle sizes (150–1250 μm), temperatures (750–920 °C), and CO2 concentrations (0–30 vol.%). The experimental data measured from MFB-TGA were analyzed using a detailed model including surface reaction and intraparticle and external diffusion. The results show that the kinetics of limestone calcination measured by MFB-TGA are faster than those measured via regular TGA. This particle-injecting method of MFB-TGA provides a new experimental idea for measuring fast calcination kinetics occurring inside fluidized bed reactors and provides guidance on the application of CaL technology. Full article
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Article
Selective Hydrogenation of 2-Methyl-3-butyn-2-ol in Microcapillary Reactor on Supported Intermetallic PdZn Catalyst, Effect of Support Doping on Stability and Kinetic Parameters
Catalysts 2022, 12(12), 1660; https://doi.org/10.3390/catal12121660 - 17 Dec 2022
Viewed by 552
Abstract
The development of active, selective, and stable multicrystalline catalytic coatings on the inner surface of microcapillary reactors addresses environmental problems of fine organic synthesis, in particular by reducing the large quantities of reagents and byproducts. Thin-film nanosized bimetallic catalysts based on mesoporous pure [...] Read more.
The development of active, selective, and stable multicrystalline catalytic coatings on the inner surface of microcapillary reactors addresses environmental problems of fine organic synthesis, in particular by reducing the large quantities of reagents and byproducts. Thin-film nanosized bimetallic catalysts based on mesoporous pure titania and doped with zirconia, ceria, and zinc oxide, for use in microreactors, were developed, and the regularities of their formation were studied. The efficiency of PdZn/TixM1−xO2±y (M = Ce, Zr, Zn) in the hydrogenation of 2-methyl-3-butyn 2-ol was studied with an emphasis on the stability of the catalyst during the reaction. The catalytic parameters depend on the adsorption properties and activity of PdZn and Pd(0) active centers. Under reaction conditions, resistance to the decomposition of PdZn is a factor that affects the stability of the catalyst. The zinc-doped coating proved to be the most selective and stable in the reaction of selective hydrogenation of acetylenic alcohols in a microcapillary reactor. This coating retained a high selectivity of 98.2% during long-term testing up to 168 h. Modification of the morphology and electronic structure of the active component, by doping titania with Ce and Zr, is accompanied by a decrease in stability. Full article
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Article
Immobilization of Glucose Oxidase on Glutathione Capped CdTe Quantum Dots for Bioenergy Generation
Catalysts 2022, 12(12), 1659; https://doi.org/10.3390/catal12121659 - 17 Dec 2022
Viewed by 699
Abstract
An efficient immobilization of Glucose oxidase (GOx) on an appropriate substrate is one of the main challenges of developing fuel cells that allow energy to be obtained from renewable substrates such as carbohydrates in physiological environments. The research importance of biofuel cells relies [...] Read more.
An efficient immobilization of Glucose oxidase (GOx) on an appropriate substrate is one of the main challenges of developing fuel cells that allow energy to be obtained from renewable substrates such as carbohydrates in physiological environments. The research importance of biofuel cells relies on their experimental robustness and high compatibility with biological organisms such as tissues or the bloodstream with the aim of obtaining electrical energy even from living systems. In this work, we report the use of 5,10,15,20 tetrakis (1-methyl-4-pyridinium) porphyrin and glutathione capped CdTe Quantum dots (GSH-CdTeQD) as a support matrix for the immobilization of GOx on carbon surfaces. Fluorescent GSH-CdTeQD particles were synthesized and their characterization by UV-Vis spectrophotometry showed a particle size between 5–7 nm, which was confirmed by DLS and TEM measurements. Graphite and Toray paper electrodes were modified by a drop coating of porphyrin, GSH-CdTeQD and GOx, and their electrochemical activity toward glucose oxidation was evaluated by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Additionally, GOx modified electrode activity was explored by scanning electrochemical microscopy, finding that near to 70% of the surface was covered with active enzyme. The modified electrodes showed a glucose sensitivity of 0.58 ± 0.01 μA/mM and an apparent Michaelis constant of 7.8 mM. The addition of BSA blocking protein maintained the current response of common interferent molecules such as ascorbic acid (AA) with less than a 5% of interference percentage. Finally, the complex electrodes were employed as anodes in a microfluidic biofuel cell (μBFC) in order to evaluate the performance in energy production. The enzymatic anodes used in the μBFC allowed us to obtain a current density of 7.53 mAcm−2 at the maximum power density of 2.30 mWcm−2; an open circuit potential of 0.57 V was observed in the biofuel cell. The results obtained suggest that the support matrix porphyrin and GSH-CdTeQD is appropriate to immobilize GOx while preserving the enzyme’s catalytic activity. The reported electrode arrangement is a viable option for bioenergy production and/or glucose quantification. Full article
(This article belongs to the Special Issue Recent Trends in Enzyme Immobilization)
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Article
Microfluidics Biocatalysis System Applied for the Synthesis of N-Substituted Benzimidazole Derivatives by Aza-Michael Addition
Catalysts 2022, 12(12), 1658; https://doi.org/10.3390/catal12121658 - 16 Dec 2022
Viewed by 385
Abstract
Benzimidazole scaffolds became an attractive subject due to their broad spectrum of pharmacological activities. In this work, a methodology was developed for the synthesis of N-substituted benzimidazole derivatives from benzimidazoles and α, β-unsaturated compounds (acrylonitriles, acrylate esters, phenyl vinyl sulfone) catalyzed by lipase [...] Read more.
Benzimidazole scaffolds became an attractive subject due to their broad spectrum of pharmacological activities. In this work, a methodology was developed for the synthesis of N-substituted benzimidazole derivatives from benzimidazoles and α, β-unsaturated compounds (acrylonitriles, acrylate esters, phenyl vinyl sulfone) catalyzed by lipase TL IM from Thermomyces lanuginosus in continuous-flow microreactors. Investigations were conducted on reaction parameters such as solvent, substrate ratio, reaction temperature, reactant donor/acceptor structures, and reaction time. The transformation is promoted by inexpensive and readily available lipase in methanol at 45 °C for 35 min. A wide range of β-amino sulfone, β-amino nitrile, and β-amino carbonyl compounds were efficiently and selectively synthesized in high yields (76–97%). All in all, a microfluidic biocatalysis system was applied to the synthesis of N-substituted benzimidazole derivatives, and could serve as a promising fast synthesis strategy for further research to develop novel and highly potent active drugs. Full article
(This article belongs to the Special Issue Biocatalysis in Organic Chemistry and Enzyme Engineering)
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Article
In Situ Growth and UV Photocatalytic Effect of ZnO Nanostructures on a Zn Plate Immersed in Methylene Blue
Catalysts 2022, 12(12), 1657; https://doi.org/10.3390/catal12121657 - 16 Dec 2022
Viewed by 440
Abstract
Nanostructures of zinc oxide (ZnO) are considered promising photocatalysts for the degradation of organic pollutants in water. This work discusses an in situ growth and UV photocatalytic effect of ZnO nanostructures on a Zn plate immersed in methylene blue (MB) at room temperature. [...] Read more.
Nanostructures of zinc oxide (ZnO) are considered promising photocatalysts for the degradation of organic pollutants in water. This work discusses an in situ growth and UV photocatalytic effect of ZnO nanostructures on a Zn plate immersed in methylene blue (MB) at room temperature. First, the Zn surfaces were pretreated via sandblasting to introduce a micro-scale roughness. Then, the Zn plates were immersed in MB and exposed to UV light, to observe ZnO nanostructure growth and photocatalytic degradation of MB. Scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and UV-Vis diffuse reflectance spectroscopy were used to characterize the Zn surfaces. We observed the growth of stoichiometric and crystalline ZnO with a nano-leaf morphology and an estimated bandgap of 3.08 eV. The photocatalytic degradation of MB was also observed in the presence of the ZnO nanostructures and UV light. The average percentage degradation was 76% in 4 h, and the degradation rate constant was 0.3535 h−1. The experimental results suggest that room temperature growth of ZnO nanostructures (on Zn surfaces) in organic dye solutions is possible. Furthermore, the nanostructured surface can be used simultaneously for the photocatalytic degradation of the organic dye. Full article
(This article belongs to the Special Issue Nanomaterials for Photocatalysis and Piezo-Photocatalysis)
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Article
Solvent Coordination Effect on Copper-Based Molecular Catalysts for Controlled Radical Polymerization
Catalysts 2022, 12(12), 1656; https://doi.org/10.3390/catal12121656 - 16 Dec 2022
Viewed by 531
Abstract
The equilibrium of copper-catalyzed atom transfer radical polymerization was investigated in silico with the aim of finding an explanation for the experimentally observed solvent effect. Various combinations of alkyl halide initiators and copper complexes in acetonitrile (MeCN) and dimethyl sulfoxide (DMSO) were taken [...] Read more.
The equilibrium of copper-catalyzed atom transfer radical polymerization was investigated in silico with the aim of finding an explanation for the experimentally observed solvent effect. Various combinations of alkyl halide initiators and copper complexes in acetonitrile (MeCN) and dimethyl sulfoxide (DMSO) were taken into consideration. A continuum model for solvation, which does not account for the explicit interactions between the solvent and metal complex, is not adequate and does not allow the reproduction of the experimental trend. However, when the solvent molecules are included in the coordination sphere of the copper(I,II) species and the continuum description of the medium is still used, a solvent dependence of process thermodynamics emerges, in fair agreement with experimental trends. Full article
(This article belongs to the Section Computational Catalysis)
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Article
Transfer Hydrogenation of Biomass-Like Phenolic Compounds and 2-PrOH over Ni-Based Catalysts Prepared Using Supercritical Antisolvent Coprecipitation
Catalysts 2022, 12(12), 1655; https://doi.org/10.3390/catal12121655 - 15 Dec 2022
Viewed by 398
Abstract
Transfer hydrogenation (TH) is considered as one of the most promising ways to convert biomass into valuable products. This study aims to demonstrate the performance of high-loaded Ni-based catalysts in the TH of phenolic compounds such as guaiacol and dimethoxybenzenes. The experiments were [...] Read more.
Transfer hydrogenation (TH) is considered as one of the most promising ways to convert biomass into valuable products. This study aims to demonstrate the performance of high-loaded Ni-based catalysts in the TH of phenolic compounds such as guaiacol and dimethoxybenzenes. The experiments were carried out under supercritical conditions at 250 °C using 2-PrOH as the only hydrogen donor. Ni-SiO2 and NiCu-SiO2 were synthesized using the eco-friendly original method based on supercritical antisolvent coprecipitation. It has been found that guaiacol is rapidly converted into 2-methoxycyclohexanol and cyclohexanol, while the presence of Cu impedes the formation of the latter product. Transformations of dimethoxybenzene position isomers are slower and result in different products. Thus, 1,3-dimethoxybenzene loses oxygen atoms transform into methoxycyclohexane and cyclohexanol, whereas the saturation of the aromatic ring is more typical for other isomers. The Cu addition increases specific catalytic activity in the TH of 1,2-and 1,3-dimethoxybenzene compared to the Cu-free catalyst. Full article
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Article
Effect of B4C/Gr on Hardness and Wear Behavior of Al2618 Based Hybrid Composites through Taguchi and Artificial Neural Network Analysis
Catalysts 2022, 12(12), 1654; https://doi.org/10.3390/catal12121654 - 15 Dec 2022
Viewed by 454
Abstract
Artificial neural networks (ANNs) have recently gained popularity as useful models for grouping, clustering, and analysis in a wide range of fields. An ANN is a kind of machine learning (ML) model that has become competitive with traditional regression and statistical models in [...] Read more.
Artificial neural networks (ANNs) have recently gained popularity as useful models for grouping, clustering, and analysis in a wide range of fields. An ANN is a kind of machine learning (ML) model that has become competitive with traditional regression and statistical models in terms of useability. Lightweight composite materials have been acknowledged to be the suitable materials, and they have been widely implemented in various industrial settings due to their adaptability. In this research exploration, hybrid composite materials using Al2618 reinforced with B4C and Gr were prepared and then evaluated for hardness and wear behavior. Reinforced alloys have a higher (approximately 36%) amount of ceramic phases than unreinforced metals. With each B4C and Gr increase, the wear resistance continued to improve. It was found that microscopic structures and an appearance of homogenous particle distribution were observed with an electron microscope, and they revealed a B4C and Gr mixed insulation surface formed as a mechanically mixed layer, and this served as an effective insulation surface that protected the test sample surface from the steel disc. The ANN and Taguchi results confirm that load contributed more to the wear rate of the composites. Full article
(This article belongs to the Special Issue Design and Synthesis of Nanostructured Catalysts)
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Article
Biodegradation of Crystalline and Nonaqueous Phase Liquid-Dissolved ATRAZINE by Arthrobacter sp. ST11 with Cd2+ Resistance
Catalysts 2022, 12(12), 1653; https://doi.org/10.3390/catal12121653 - 15 Dec 2022
Viewed by 400
Abstract
A newly isolated cadmium (Cd)-resistant bacterial strain from herbicides-polluted soil in China could use atrazine as the sole carbon, nitrogen, and energy source for growth in a mineral salt medium (MSM). Based on 16S rRNA gene sequence analysis and physiochemical tests, the bacterium [...] Read more.
A newly isolated cadmium (Cd)-resistant bacterial strain from herbicides-polluted soil in China could use atrazine as the sole carbon, nitrogen, and energy source for growth in a mineral salt medium (MSM). Based on 16S rRNA gene sequence analysis and physiochemical tests, the bacterium was identified as Arthrobacter sp. and named ST11. The biodegradation of atrazine by ST11 was investigated in experiments, with the compound present either as crystals or dissolved in di(2-ethylhexyl) phthalate (DEHP) as a non-aqueous phase liquid (NAPL). After 48 h, ST11 consumed 68% of the crystalline atrazine in MSM. After being dissolved in DEHP, the degradation ratio of atrazine was reduced to 55% under the same conditions. Obviously, the NAPL-dissolved atrazine has lower bioavailability than the crystalline atrazine. Cd2+ at concentrations of 0.05–1.5 mmol/L either had no effect (<0.3 mmol/L), slight effects (0.5–1.0 mmol/L), or significantly (1.5 mmol/L) inhibited the growth of ST11 in Luria-Bertani medium. Correspondingly, in the whole concentration range (0.05–1.5 mmol/L), Cd2+ promoted ST11 to degrade atrazine, whether crystalline or dissolved in DEHP. Refusal to adsorb Cd2+ may be the main mechanism of high Cd resistance in ST11 cells. These results may provide valuable insights for the microbial treatment of arable soil co-polluted by atrazine and Cd. Full article
(This article belongs to the Special Issue Microbes Biocatalysis)
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Article
Fusion-Assisted Hydrothermal Synthesis and Post-Synthesis Modification of Mesoporous Hydroxy Sodalite Zeolite Prepared from Waste Coal Fly Ash for Biodiesel Production
Catalysts 2022, 12(12), 1652; https://doi.org/10.3390/catal12121652 - 15 Dec 2022
Viewed by 414
Abstract
Increases in biodiesel prices remains a challenge, mainly due to the high cost of conventional oil feedstocks used during biodiesel production and the challenges associated with using homogeneous catalysts in the process. This study investigated the conversion of waste-derived black soldier fly (BSF) [...] Read more.
Increases in biodiesel prices remains a challenge, mainly due to the high cost of conventional oil feedstocks used during biodiesel production and the challenges associated with using homogeneous catalysts in the process. This study investigated the conversion of waste-derived black soldier fly (BSF) maggot oil feedstock over hydroxy sodalite (HS) zeolite synthesized from waste coal fly ash (CFA) in biodiesel production. The zeolite product prepared after fusion of CFA followed by hydrothermal synthesis (F-HS) resulted in a highly crystalline, mesoporous F-HS zeolite with a considerable surface area of 45 m2/g. The impact of post-synthesis modification of the parent HS catalyst (F-HS) by ion exchange with an alkali source (KOH) on its performance in biodiesel production was investigated. The parent F-HS zeolite catalyst resulted in a high biodiesel yield of 84.10%, with a good quality of 65% fatty acid methyl ester (FAME) content and fuel characteristics compliant with standard biodiesel specifications. After ion exchange, the modified HS zeolite catalyst (K/F-HS) decreased in crystallinity, mesoporosity and total surface area. The K/F-HS catalyst resulted in sub-standard biodiesel of 51.50% FAME content. Hence, contrary to various studies, the ion exchange modified zeolite was unfavorable as a catalyst for biodiesel production. Interestingly, the F-HS zeolite derived from waste CFA showed a favorable performance as a heterogeneous catalyst compared to the conventional sodium hydroxide (NaOH) homogeneous catalyst. The zeolite catalyst resulted in a more profitable process using BSF maggot oil and was economically comparable with NaOH for every kilogram of biodiesel produced. Furthermore, this study showed the potential to address the overall biodiesel production cost challenge via the development of waste-derived catalysts and BSF maggot oil as low-cost feedstock alternatives. Full article
(This article belongs to the Special Issue Environmental Catalytic Applications of Waste-Derived Materials)
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Review
Catalytic Hydropyrolysis of Lignin for the Preparation of Cyclic Hydrocarbon-Based Biofuels
Catalysts 2022, 12(12), 1651; https://doi.org/10.3390/catal12121651 - 15 Dec 2022
Viewed by 669
Abstract
The demand for biomass utilization is increasing because of the depletion of fossil resources that are non-renewable in nature. Lignin is the second most renewable organic carbon source, but currently it has limited scope for application in the chemical and fuel industries. Lignin [...] Read more.
The demand for biomass utilization is increasing because of the depletion of fossil resources that are non-renewable in nature. Lignin is the second most renewable organic carbon source, but currently it has limited scope for application in the chemical and fuel industries. Lignin is a side product of the paper and pulp, sugar, and 2G bioethanol industries. Many research groups are working on the value-addition of lignin. Among the lignin depolymerization methods, catalytic hydropyrolysis is gaining attention and is playing a crucial role in developing biorefinery. The hydropyrolysis of lignin was conducted at a higher temperature in the presence of H2. The hydropyrolysis of lignin results in the selective formation of non-oxygenated cyclic hydrocarbons in a shorter reaction time. It is possible to use the cyclic hydrocarbons directly as a fuel or they can be blended with conventional gasoline. This review focuses on the prior art of pyrolysis and hydropyrolysis of lignin. Possible products of lignin hydropyrolysis and suitable synthetic routes to obtain non-oxygenated cyclic hydrocarbons are also discussed. The influence of various process parameters, such as type of reactor, metal catalyst, nature of catalytic supports, reaction temperature, and H2 pressure are discussed with regard to the hydropyrolysis of lignin to achieve good selectivity of cyclic hydrocarbons. Full article
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Article
Ni5P4-NiP2-Ni2P Nanocomposites Tangled with N-Doped Carbon for Enhanced Electrochemical Hydrogen Evolution in Acidic and Alkaline Solutions
Catalysts 2022, 12(12), 1650; https://doi.org/10.3390/catal12121650 - 15 Dec 2022
Viewed by 519
Abstract
Heterostructured non-precious metal phosphides have attracted increasing attention in the development of high-performance catalysts for hydrogen evolution reaction (HER), particularly in acidic media. Herein, a catalyst composed of ternary Ni5P4-NiP2-Ni2P nanocomposites and N-doped carbon nanotubes/carbon [...] Read more.
Heterostructured non-precious metal phosphides have attracted increasing attention in the development of high-performance catalysts for hydrogen evolution reaction (HER), particularly in acidic media. Herein, a catalyst composed of ternary Ni5P4-NiP2-Ni2P nanocomposites and N-doped carbon nanotubes/carbon particulates (Ni5P4-NiP2-Ni2P/NC) was prepared from a Ni-containing hybrid precursor through approaches of a successive carbonization and phosphating reaction. Benefiting from the synergistic effect from three-component nickel phosphides and the support role of porous carbon network, the Ni5P4-NiP2-Ni2P/N-doped carbon catalyst presents the promising HER performance with overpotentials of 168 and 202 mV at the current density of 10 mA cm−2 and Tafel slopes of 69.0 and 74 mV dec−1 in both acidic and alkaline solutions, respectively, which surpasses the Ni2P/N-doped carbon counterpart. This work provides an effective strategy for the preparation and development of highly efficient HER non-precious metal electrocatalysts by creating heterostructure in acidic and alkaline media. Full article
(This article belongs to the Special Issue Transition Metal Complexes as Catalysts)
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Article
Enhancing the Thermal Stability of Glutathione Bifunctional Synthase by B-Factor Strategy and Un/Folding Free Energy Calculation
Catalysts 2022, 12(12), 1649; https://doi.org/10.3390/catal12121649 - 15 Dec 2022
Viewed by 332
Abstract
Glutathione is of great significance in pharmaceutical and health fields, and one-step synthesis of reduced glutathione by glutathione bifunctional synthase has become a focus of research. The stability of glutathione bifunctional synthase is generally poor and urgently needs to be modified. The B-factor [...] Read more.
Glutathione is of great significance in pharmaceutical and health fields, and one-step synthesis of reduced glutathione by glutathione bifunctional synthase has become a focus of research. The stability of glutathione bifunctional synthase is generally poor and urgently needs to be modified. The B-factor strategy and un/folding free energy calculation were both applied to enhance the thermal stability of glutathione bifunctional synthase from Streptococcus agalactiae (GshFSA). Based on the concept of B-factor strategy, we calculated the B-factor by molecular dynamics simulation to find flexible residues, performed point saturation mutations and high-throughput screening. At the same time, we also calculated the un/folding free energy of GshFSA and performed the point mutations. The optimal mutant from the B-factor strategy was R270S, which had a 2.62-fold increase in half-life period compared to the wild type, and the Q406M was the optimal mutant from the un/folding free energy calculation, with a 3.02-fold increase in half-life period. Both of them have provided a mechanistic explanation. Full article
(This article belongs to the Special Issue High-Throughput Computational Design of Catalysts)
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Article
CO2 Hydrogenation to Renewable Methane on Ni/Ru Modified ZSM-5 Zeolites: The Role of the Preparation Procedure
Catalysts 2022, 12(12), 1648; https://doi.org/10.3390/catal12121648 - 15 Dec 2022
Viewed by 474
Abstract
Mono- and bimetallic Ni- and Ru-modified micro-mesoporous ZSM-5 catalysts were prepared by wet impregnation. The influence of the Ni content, the addition of Ru and the sequence of the modification by two metals on the physicochemical properties of the catalysts were studied. They [...] Read more.
Mono- and bimetallic Ni- and Ru-modified micro-mesoporous ZSM-5 catalysts were prepared by wet impregnation. The influence of the Ni content, the addition of Ru and the sequence of the modification by two metals on the physicochemical properties of the catalysts were studied. They were characterized by X-ray powder diffraction (XRD), N2 physisorption, temperature-programmed reduction (TPR-TGA), TEM and XPS spectroscopy. Formation of finely dispersed nickel and/or ruthenium oxide species was observed on the external surface and in the pores of zeolite support. It was found that the peculiarity of the used zeolite structure and the modification procedure determine the type of formed metal oxides, their dispersion and reducibility. XPS study revealed that the surface became rich in nickel and poorer in ruthenium for bimetallic catalysts. Ni had higher dispersion in the presence of ruthenium, and TPR investigations also confirmed its facilitated reducibility. The studied catalysts were tested in CO2 hydrogenation to methane. 10Ni5RuZSM-5 material showed the highest activity and high selectivity for methane formation, reaching the equilibrium conversion and 100% selectivity at 400 °C. Stability and reusability of the latter catalyst show that it is appropriate for practical application. Full article
(This article belongs to the Special Issue Catalysis on Zeolites and Zeolite-Like Materials II)
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