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Catalysts, Volume 11, Issue 2 (February 2021) – 150 articles

Cover Story (view full-size image): The performance of an immobilized photocatalyst has been successfully improved by colloidal processing of a heterostructure composed by TiO2 nanoparticles and lignocellulose nanofibers (LCNF) obtained from biomass residues. View this paper
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Open AccessArticle
Valorization of Raw and Calcined Chicken Eggshell for Sulfur Dioxide and Hydrogen Sulfide Removal at Low Temperature
Catalysts 2021, 11(2), 295; https://doi.org/10.3390/catal11020295 - 23 Feb 2021
Viewed by 489
Abstract
Chicken eggshell (ES) is a waste from the food industry with a high calcium content produced in substantial quantity with very limited recycling. In this study, eco-friendly sorbents from raw ES and calcined ES were tested for sulfur dioxide (SO2) and [...] Read more.
Chicken eggshell (ES) is a waste from the food industry with a high calcium content produced in substantial quantity with very limited recycling. In this study, eco-friendly sorbents from raw ES and calcined ES were tested for sulfur dioxide (SO2) and hydrogen sulfide (H2S) removal. The raw ES was tested for SO2 and H2S adsorption at different particle size, with and without the ES membrane layer. Raw ES was then subjected to calcination at different temperatures (800 °C to 1100 °C) to produce calcium oxide. The effect of relative humidity and reaction temperature of the gases was also tested for raw and calcined ES. Characterization of the raw, calcinated and spent sorbents confirmed that calcined eggshell CES (900 °C) showed the best adsorption capacity for both SO2 (3.53 mg/g) and H2S (2.62 mg/g) gas. Moreover, in the presence of 40% of relative humidity in the inlet gas, the adsorption capacity of SO2 and H2S gases improved greatly to about 11.68 mg/g and 7.96 mg/g respectively. Characterization of the raw and spent sorbents confirmed that chemisorption plays an important role in the adsorption process for both pollutants. The results indicated that CES can be used as an alternative sorbent for SO2 and H2S removal. Full article
(This article belongs to the Special Issue Catalysts and Processes for H2S Conversion to Sulfur)
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Open AccessFeature PaperReview
Photoactive Heterostructures: How They Are Made and Explored
Catalysts 2021, 11(2), 294; https://doi.org/10.3390/catal11020294 - 23 Feb 2021
Viewed by 443
Abstract
In our review we consider the results on the development and exploration of heterostructured photoactive materials with major attention focused on what are the better ways to form this type of materials and how to explore them correctly. Regardless of what type of [...] Read more.
In our review we consider the results on the development and exploration of heterostructured photoactive materials with major attention focused on what are the better ways to form this type of materials and how to explore them correctly. Regardless of what type of heterostructure, metal–semiconductor or semiconductor–semiconductor, is formed, its functionality strongly depends on the quality of heterojunction. In turn, it depends on the selection of the heterostructure components (their chemical and physical properties) and on the proper choice of the synthesis method. Several examples of the different approaches such as in situ and ex situ, bottom-up and top-down, are reviewed. At the same time, even if the synthesis of heterostructured photoactive materials seems to be successful, strong experimental physical evidence demonstrating true heterojunction formation are required. A possibility for obtaining such evidence using different physical techniques is discussed. Particularly, it is demonstrated that the ability of optical spectroscopy to study heterostructured materials is in fact very limited. At the same time, such experimental techniques as high-resolution transmission electron microscopy (HRTEM) and electrophysical methods (work function measurements and impedance spectroscopy) present a true signature of heterojunction formation. Therefore, whatever the purpose of heterostructure formation and studies is, the application of HRTEM and electrophysical methods is necessary to confirm that formation of the heterojunction was successful. Full article
(This article belongs to the Special Issue Photocatalytic Nanocomposite Materials)
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Open AccessFeature PaperArticle
Solid-State Synthesis of Direct Z-Scheme Cu2O/WO3 Nanocomposites with Enhanced Visible-Light Photocatalytic Performance
Catalysts 2021, 11(2), 293; https://doi.org/10.3390/catal11020293 - 23 Feb 2021
Viewed by 476
Abstract
In this paper, we report the preparation of visible-light active direct Z-scheme Cu2O/WO3 nanocomposite photocatalyst by a solid-state reaction avoiding the otherwise inevitable formation of CuWO4 phase in wet syntheses. Structure, morphology, and thermal and optical properties of prepared [...] Read more.
In this paper, we report the preparation of visible-light active direct Z-scheme Cu2O/WO3 nanocomposite photocatalyst by a solid-state reaction avoiding the otherwise inevitable formation of CuWO4 phase in wet syntheses. Structure, morphology, and thermal and optical properties of prepared WO3 nanoplatelets decorated by Cu2O were investigated by XRD, Raman spectroscopy, SEM/TEM, combined thermogravimetric (TG)/differential scanning calorimetry (DSC) analysis, and UV–VIS spectroscopy. The photocatalytic performance of the prepared samples under UV and visible light was studied through monitoring discoloration of methylene blue under illumination by selected wavelengths, allowing for the distinguishing between the contributions of the two semiconductive components. Experimental results showed that the decoration of WO3 nanoplates by Cu2O nanoparticles led to an improvement in photocatalytic performance, regardless of used LED (Light-Emitting Diode) wavelength, even at low concentrations. By using scavengers selectively blocking reactive species involved in the discoloration reaction, we determined that the Cu2O/WO3 nanocomposite exhibited the characteristics of direct Z-scheme-type photocatalyst. Full article
(This article belongs to the Special Issue Direct Z-Scheme Photocatalysts)
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Open AccessReview
Heterogeneous Ru Catalysts as the Emerging Potential Superior Catalysts in the Selective Hydrogenation of Bio-Derived Levulinic Acid to γ-Valerolactone: Effect of Particle Size, Solvent, and Support on Activity, Stability, and Selectivity
Catalysts 2021, 11(2), 292; https://doi.org/10.3390/catal11020292 - 23 Feb 2021
Viewed by 572
Abstract
Catalytic hydrogenation of a biomass-derived molecule, levulinic acid (LA), to γ-valerolactone (GVL) has been getting much attention from researchers across the globe recently. This is because GVL has been identified as one of the potential molecules for replacing fossil fuels. For instance, GVL [...] Read more.
Catalytic hydrogenation of a biomass-derived molecule, levulinic acid (LA), to γ-valerolactone (GVL) has been getting much attention from researchers across the globe recently. This is because GVL has been identified as one of the potential molecules for replacing fossil fuels. For instance, GVL can be catalytically converted into liquid alkenes in the molecular weight range close to that found in transportation fuels via a process that does not require an external hydrogen source. Noble and non-noble metals have been used as catalysts for the selective hydrogenation of LA to GVL. Of these, Ru has been reported to be the most active metal for this reaction. The type of metal supports and solvents has been proved to affect the activity, selectivity, and yields of GVL. Water has been identified as a potential, effective “green” solvent for the hydrogenation of LA to GVL. The use of different sources of H2 other than molecular hydrogen (such as formic acid) has also been explored. In a few instances, the product, GVL, is hydrogenated further to other useful products such as 1,4-pentanediol (PD) and methyl tetrahydrofuran (MTHF). This review selectively focuses on the potential of immobilized Ru catalysts as a potential superior catalyst for selective hydrogenation of LA to GVL. Full article
(This article belongs to the Special Issue Biomass Valorization)
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Open AccessFeature PaperReview
Recent Applications of Heteropolyacids and Related Compounds in Heterocycle Synthesis. Contributions between 2010 and 2020
Catalysts 2021, 11(2), 291; https://doi.org/10.3390/catal11020291 - 23 Feb 2021
Viewed by 734
Abstract
Over the past two decades, polyoxometalates (POM) have received considerable attention as solid catalysts, due to their unique physicochemical characteristics, since, first, they have very strong Bronsted acidity, approaching the region of a superacid, and second, they are efficient oxidizers that exhibit rapid [...] Read more.
Over the past two decades, polyoxometalates (POM) have received considerable attention as solid catalysts, due to their unique physicochemical characteristics, since, first, they have very strong Bronsted acidity, approaching the region of a superacid, and second, they are efficient oxidizers that exhibit rapid redox transformations under fairly mild conditions. Their structural mobility is also highlighted, since they are complex molecules that can be modified by changing their structure or the elements that compose them to model their size, charge density, redox potentials, acidity, and solubility. Finally, they can be used in substoichiometric amounts and reused without an appreciable loss of catalytic activity, all of which postulate them as versatile, economic and ecological catalysts. Therefore, in 2009, we wrote a review article highlighting the great variety of organic reactions, mainly in the area of the synthesis of bioactive heterocycles in which they can be used, and this new review completes that article with the contributions made in the same area for the period 2010 to 2020. The synthesized heterocycles to be covered include pyrimidines, pyridines, pyrroles, indoles, chromenes, xanthenes, pyrans, azlactones, azoles, diazines, azepines, flavones, and formylchromones, among others. Full article
(This article belongs to the Special Issue Catalysts for the Synthesis of Heterocyclic Compounds)
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Open AccessFeature PaperArticle
Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO4-Sepiolite Supports
Catalysts 2021, 11(2), 289; https://doi.org/10.3390/catal11020289 - 22 Feb 2021
Viewed by 444
Abstract
In this work, the covalent immobilization of two ruthenium(II) complexes, i.e., [RuIICl (bpea){(S)(-)(BINAP)}](BF4), 1, and [RuIICl(bpea)(DPPE)](BF4), 2, where BINAP = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl and DPPE = 1,2-bis(diphenylphosphino)ethane, have been obtained (AlPO4[email protected]1 and AlPO [...] Read more.
In this work, the covalent immobilization of two ruthenium(II) complexes, i.e., [RuIICl (bpea){(S)(-)(BINAP)}](BF4), 1, and [RuIICl(bpea)(DPPE)](BF4), 2, where BINAP = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl and DPPE = 1,2-bis(diphenylphosphino)ethane, have been obtained (AlPO4[email protected]1 and AlPO4[email protected]2) by using a N-tridentate ligand N,N-bis-(2-pyridylmethyl)ethylamine (bpea), linked to an amorphous AlPO4-Sepiolite (20/80) inorganic support. This AlPO4-sepiolite support is able to immobilize the double amount of ruthenium complex (1.65%) than the amorphous AlPO4 (0.89%). Both heterogenized complexes have been assessed as catalysts in the liquid phase hydrogenation of several substrates with carbonyl and/or olefinic double bonds using methanol as solvent, attaining good catalytic activity and high enantioselectivity (99%). The highest Turn Over Number (TON) value (748.6) was obtained over the [RuII Cl (bpea)(DPPE)](BF4) 2 catalyst, although the [RuIICl(bpea){(S)(-)(BINAP)}](BF4) 1 exhibits better reusability. In fact, the [RuIICl(bpea){(S)(-)(BINAP)}](BF4) immobilized on AlPO4-Sepiolite maintained the activity throughout 14 successive runs. Furthermore, some findings on hydrogenation mechanisms of the α,β-unsaturated carbonyl compounds over Ru catalysts have been also obtained. Full article
(This article belongs to the Special Issue Recent Advances in Organometallic Chemistry and Catalysis)
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Open AccessEditorial
Nanocatalysts for Hydrogen Production
Catalysts 2021, 11(2), 288; https://doi.org/10.3390/catal11020288 - 22 Feb 2021
Viewed by 478
Abstract
Rising concerns about the effects of global warming and climate change have led to a search for environmentally clean and energy efficient technologies. Hydrogen is one of the most popular new types of energy, which is considered as a clean energy carrier for [...] Read more.
Rising concerns about the effects of global warming and climate change have led to a search for environmentally clean and energy efficient technologies. Hydrogen is one of the most popular new types of energy, which is considered as a clean energy carrier for the future. Hydrogen is primarily produced by the steam reforming of natural gas. Other methods have also been developed, such as the gasification of coal/biomass/waste, water splitting by electrolysis, and so on. All the ways are using nanocatalysts to obtain a high efficiency of hydrogen production [...] Full article
(This article belongs to the Special Issue Nanocatalysts for Hydrogen Production)
Open AccessArticle
Facile Synthesis of COF-Supported Reduced Pd-Based Catalyst for One-Pot Reductive Amination of Aldehydes
Catalysts 2021, 11(2), 287; https://doi.org/10.3390/catal11020287 - 22 Feb 2021
Viewed by 495
Abstract
Dibenzylamine motifs are an important class of crucial organic compounds and are widely used in fine chemical and pharmaceutical industries. The development of the efficient, economical, and environmentally friendly synthesis of amines using transition metal-based heterogeneous catalysts remains both desirable and challenging. Herein, [...] Read more.
Dibenzylamine motifs are an important class of crucial organic compounds and are widely used in fine chemical and pharmaceutical industries. The development of the efficient, economical, and environmentally friendly synthesis of amines using transition metal-based heterogeneous catalysts remains both desirable and challenging. Herein, we prepared the covalent organic framework (COF)-supported heterogeneous reduced COF-supported Pd-based catalyst and used it for the one-pot reductive amination of aldehydes. There are both Pd metallic state and oxidated Pdσ+ in the catalysts. Furthermore, in the presence of the reduced COF-supported Pd-based catalyst, many aromatic, aliphatic, and heterocyclic aldehydes with various functional groups substituted were converted to their corresponding amines products in good to excellent selectivity (up to 91%) under mild reaction conditions (70 °C, 2 h, NH3, 20 bar H2). This work expands the covalent organic frameworks for the material family and its support catalyst, opening up new catalytic applications in the economical, practical, and effective synthesis of secondary amines. Full article
(This article belongs to the Special Issue Facing Social Concerns in the 2020s: New Trends in Catalytic Polymers)
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Open AccessArticle
A Computational Method to Predict Effects of Residue Mutations on the Catalytic Efficiency of Hydrolases
Catalysts 2021, 11(2), 286; https://doi.org/10.3390/catal11020286 - 22 Feb 2021
Viewed by 449
Abstract
With scientific and technological advances, growing research has focused on engineering enzymes that acquire enhanced efficiency and activity. Thereinto, computer-based enzyme modification makes up for the time-consuming and labor-intensive experimental methods and plays a significant role. In this study, for the first time, [...] Read more.
With scientific and technological advances, growing research has focused on engineering enzymes that acquire enhanced efficiency and activity. Thereinto, computer-based enzyme modification makes up for the time-consuming and labor-intensive experimental methods and plays a significant role. In this study, for the first time, we collected and manually curated a data set for hydrolases mutation, including structural information of enzyme-substrate complexes, mutated sites and Kcat/Km obtained from vitro assay. We further constructed a classification model using the random forest algorithm to predict the effects of residue mutations on catalytic efficiency (increase or decrease) of hydrolases. This method has achieved impressive performance on a blind test set with the area under the receiver operating characteristic curve of 0.86 and the Matthews Correlation Coefficient of 0.659. Our results demonstrate that computational mutagenesis has an instructive effect on enzyme modification, which may expedite the design of engineering hydrolases. Full article
(This article belongs to the Section Computational Catalysis)
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Open AccessEditorial
Editorial: Special Issue on “Emerging Nanostructured Catalytic Materials for Energy and Environmental Applications”
Catalysts 2021, 11(2), 285; https://doi.org/10.3390/catal11020285 - 22 Feb 2021
Viewed by 443
Abstract
In recent years, there has been a great demand for the rational design and development of novel catalytic materials at the nanoscale (1–100 nm), with a view to more accurately and efficiently control reaction pathways due to their high surface area and intrinsic [...] Read more.
In recent years, there has been a great demand for the rational design and development of novel catalytic materials at the nanoscale (1–100 nm), with a view to more accurately and efficiently control reaction pathways due to their high surface area and intrinsic properties [...] Full article
Open AccessFeature PaperReview
Sonochemical and Sonoelectrochemical Production of Energy Materials
Catalysts 2021, 11(2), 284; https://doi.org/10.3390/catal11020284 - 21 Feb 2021
Viewed by 651
Abstract
Sonoelectrochemistry is the combination of ultrasound and electrochemistry which provides many advantages in electrochemistry, such as fast reaction rates, surface cleaning and activation, and increased mass transport at an electrode. Due to the advantages, some efforts have been made in order to benefit [...] Read more.
Sonoelectrochemistry is the combination of ultrasound and electrochemistry which provides many advantages in electrochemistry, such as fast reaction rates, surface cleaning and activation, and increased mass transport at an electrode. Due to the advantages, some efforts have been made in order to benefit sonoelectrochemistry in the field of energy and environmental engineering. This review paper highlights the developed progress of the application of sonoelectrochemistry in the production of hydrogen, electrocatalyst materials and electrodes for fuel cells and semiconductor photocatalyst materials. This review also provides the experimental methods that are utilized in several sonoelectrochemical techniques, such as different set-ups generally used for the synthesis of energy-related materials. Different key parameters in the operation of sonoelectrochemical synthesis including ultrasonication time, ultrasound frequency and operation current have been also discussed. There are not many research articles on the sonoelectrochemical production of materials for supercapacitors and water electrolyzers which play crucial roles in the renewable energy industry. Therefore, at the end of this review, some articles which have reported the use of ultrasound for the production of electrocatalysts for supercapacitors and electrolyzers have been reviewed. The current review might be helpful for scientists and engineers who are interested in and working on sonoelectrochemistry and electrocatalyst synthesis for energy storage and energy conversion. Full article
(This article belongs to the Special Issue Catalysis Under Ultrasonic Irradiation)
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Open AccessFeature PaperPerspective
Metal-Organic Frameworks in Oxidation Catalysis with Hydrogen Peroxide
Catalysts 2021, 11(2), 283; https://doi.org/10.3390/catal11020283 - 21 Feb 2021
Viewed by 620
Abstract
In recent years, metal–organic frameworks (MOFs) have received increasing attention as selective oxidation catalysts and supports for their construction. In this short review paper, we survey recent findings concerning use of MOFs in heterogeneous liquid-phase selective oxidation catalysis with the green oxidant–aqueous hydrogen [...] Read more.
In recent years, metal–organic frameworks (MOFs) have received increasing attention as selective oxidation catalysts and supports for their construction. In this short review paper, we survey recent findings concerning use of MOFs in heterogeneous liquid-phase selective oxidation catalysis with the green oxidant–aqueous hydrogen peroxide. MOFs having outstanding thermal and chemical stability, such as Cr(III)-based MIL-101, Ti(IV)-based MIL-125, Zr(IV)-based UiO-66(67), Zn(II)-based ZIF-8, and some others, will be in the main focus of this work. The effects of the metal nature and MOF structure on catalytic activity and oxidation selectivity are analyzed and the mechanisms of hydrogen peroxide activation are discussed. In some cases, we also make an attempt to analyze relationships between liquid-phase adsorption properties of MOFs and peculiarities of their catalytic performance. Attempts of using MOFs as supports for construction of single-site catalysts through their modification with heterometals will be also addressed in relation to the use of such catalysts for activation of H2O2. Special attention is given to the critical issues of catalyst stability and reusability. The scope and limitations of MOF catalysts in H2O2-based selective oxidation are discussed. Full article
(This article belongs to the Special Issue Heterogeneous Selective and Total Catalytic Oxidation)
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Open AccessFeature PaperArticle
Transformation of Dilute Ethylene at High Temperature on Micro- and Nano-Sized H-ZSM-5 Zeolites
Catalysts 2021, 11(2), 282; https://doi.org/10.3390/catal11020282 - 21 Feb 2021
Viewed by 526
Abstract
Ethylene dehydroaromatisation (EDA) was investigated at 700 °C under 1 bar of ethylene (5 mol% in N2) over a micro-(M) and a nano-sized (N) H-ZSM-5. On the M zeolite an induction period followed by deactivation was observed, which could be related [...] Read more.
Ethylene dehydroaromatisation (EDA) was investigated at 700 °C under 1 bar of ethylene (5 mol% in N2) over a micro-(M) and a nano-sized (N) H-ZSM-5. On the M zeolite an induction period followed by deactivation was observed, which could be related to the presence of long diffusion path lengths in this sample, leading to mass transfer resistance. During the induction step, the aromatics yield increases, despite a significant loss of the acid site concentration as a result of coking. This induction period corresponds to the formation of an active hydrocarbon pool (HCP) composed of units of 2 to 5 aromatic rings with a molecular weight ranging from 130 to 220 g mol−1 (light coke). A kinetic study revealed that the developing HCP species is two times more active than Brønsted acid sites in the fresh zeolite. Diffusion limitations yet impact the product desorption by promoting coke growth and, therefore the deactivation of the HCP and hence of the catalyst. From MA-LDI/LDI-TOF MS (Matrix Assisted Laser Desorption Ionization—Time of Flight Mass Spectroscopy) characterisation was deduced that even after complete catalyst deactivation, the as-deposited coke continues growing at the external surface of the zeolite by condensation reactions, thus leading to heavy coke composed of more than 100 carbon atoms and a molar mass exceeding 1300 g mol−1. Unlike the micro-sized zeolite, the nano-scaled zeolite features a short diffusion path length and promotes fast formation of the active HCP. As a result, higher activity and selectivity into benzene were observed, whilst catalyst deactivation was significantly mitigated. Full article
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Open AccessArticle
Na3[Ru2(µ-CO3)4] as a Homogeneous Catalyst for Water Oxidation; HCO3 as a Co-Catalyst
Catalysts 2021, 11(2), 281; https://doi.org/10.3390/catal11020281 - 21 Feb 2021
Viewed by 931
Abstract
In neutral medium (pH 7.0) [RuIIIRuII(µ-CO3)4(OH)]4− undergoes one electron oxidation to form [RuIIIRuIII(µ-CO3)4(OH)2]4− at an E1/2 of 0.85 [...] Read more.
In neutral medium (pH 7.0) [RuIIIRuII(µ-CO3)4(OH)]4− undergoes one electron oxidation to form [RuIIIRuIII(µ-CO3)4(OH)2]4− at an E1/2 of 0.85 V vs. NHE followed by electro-catalytic water oxidation at a potential ≥1.5 V. When the same electrochemical measurements are performed in bicarbonate medium (pH 8.3), the complex first undergoes one electron oxidation at an Epa of 0.86 V to form [RuIIIRuIII(µ-CO3)4(OH)2]4−. This complex further undergoes two step one electron oxidations to form RuIVRuIII and RuIVRuIV species at potentials (Epa) 1.18 and 1.35 V, respectively. The RuIVRuIII and RuIVRuIV species in bicarbonate solutions are [RuIVRuIII(µ-CO3)4(OH)(CO3)]4− and [RuIVRuIV(µ-CO3)4(O)(CO3)]4− based on density functional theory (DFT) calculations. The formation of HCO4 in the course of the oxidation has been demonstrated by DFT. The catalyst acts as homogeneous water oxidation catalyst, and after long term chronoamperometry, the absorption spectra does not change significantly. Each step has been found to follow a proton coupled electron transfer process (PCET) as obtained from the pH dependent studies. The catalytic current is found to follow linear relation with the concentration of the catalyst and bicarbonate. Thus, bicarbonate is involved in the catalytic process that is also evident from the generation of higher oxidation peaks in cyclic voltammetry. The detailed mechanism has been derived by DFT. A catalyst with no organic ligands has the advantage of long-time stability. Full article
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Open AccessFeature PaperReview
A Focus on the Transformation Processes for the Valorization of Glycerol Derived from the Production Cycle of Biofuels
Catalysts 2021, 11(2), 280; https://doi.org/10.3390/catal11020280 - 20 Feb 2021
Viewed by 477
Abstract
Glycerol is a valuable by-product in the biodiesel industries. However, the increase in biodiesel production resulted in an excess production of glycerol, with a limited market compared to its availability. Precisely because glycerol became a waste to be disposed of, the costs of [...] Read more.
Glycerol is a valuable by-product in the biodiesel industries. However, the increase in biodiesel production resulted in an excess production of glycerol, with a limited market compared to its availability. Precisely because glycerol became a waste to be disposed of, the costs of biodiesel production have reduced. From an environmental point of view, identifying reactions that can convert glycerol into new products that can be reused in different applications has become a real necessity. According to the unique structural characteristics of glycerol, transformation processes can lead to different chemical functionalities through redox reactions, dehydration, esterification, and etherification, with the formation of products that can be applied both at the finest chemical level and to bulk chemistry. Full article
(This article belongs to the Special Issue Catalytic Processes in Biofuel Production and Biomass Valorization)
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Open AccessReview
Recent Developments for the Application of 3D Structured Material Nickel Foam and Graphene Foam in Direct Liquid Fuel Cells and Electrolyzers
Catalysts 2021, 11(2), 279; https://doi.org/10.3390/catal11020279 - 19 Feb 2021
Viewed by 499
Abstract
Platinum and platinum-based catalysts are some of the most effective catalysts used in fuel cells. However, electrocatalysts used for direct liquid fuel cells (DLFCs) and electrolyzers are high cost and suffer from several other problems, thus hindering their commercialization as power sources to [...] Read more.
Platinum and platinum-based catalysts are some of the most effective catalysts used in fuel cells. However, electrocatalysts used for direct liquid fuel cells (DLFCs) and electrolyzers are high cost and suffer from several other problems, thus hindering their commercialization as power sources to produce clean energy. Common issues in electrocatalysts are low stability and durability, slow kinetics, catalyst poisoning, high catalyst loading, high cost of the catalytic materials, poisoning of the electrocatalysts, and formation of intermediate products during electrochemical reactions. The use of catalyst supports can enhance the catalytic activity and stability of the power sources. Thus, nickel foam and graphene foam with 3D structures have advantages over other catalyst supports. This paper presents the application of nickel foam and graphene foam as catalyst supports that enhance the activities, selectivity, efficiency, specific surface area, and exposure of the active sites of DLFCs. Selected recent studies on the use of foam in electrolyzers are also presented. Full article
(This article belongs to the Section Electrocatalysis)
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Open AccessReview
Status Update on Bioelectrochemical Systems: Prospects for Carbon Electrode Design and Scale-Up
Catalysts 2021, 11(2), 278; https://doi.org/10.3390/catal11020278 - 19 Feb 2021
Viewed by 502
Abstract
Bioelectrochemical systems (BES) employ enzymes, subcellular structures or whole electroactive microorganisms as biocatalysts for energy conversion purposes, such as the electrosynthesis of value-added chemicals and power generation in biofuel cells. From a bioelectrode engineering viewpoint, customizable nanostructured carbonaceous matrices have recently received considerable [...] Read more.
Bioelectrochemical systems (BES) employ enzymes, subcellular structures or whole electroactive microorganisms as biocatalysts for energy conversion purposes, such as the electrosynthesis of value-added chemicals and power generation in biofuel cells. From a bioelectrode engineering viewpoint, customizable nanostructured carbonaceous matrices have recently received considerable scientific attention as promising electrode supports due to their unique properties attractive to bioelectronics devices. This review demonstrates the latest advances in the application of nano- and micro-structured carbon electrode assemblies in BES. Specifically, in view of the gradual increase in the commercial applicability of these systems, we aim to address the stability and scalability of different BES designs and to highlight their potential roles in a circular bioeconomy. Full article
(This article belongs to the Special Issue NanoBio Hybrids and Photocatalysis)
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Open AccessReview
Hierarchical Ternary Sulfides as Effective Photocatalyst for Hydrogen Generation Through Water Splitting: A Review on the Performance of ZnIn2S4
Catalysts 2021, 11(2), 277; https://doi.org/10.3390/catal11020277 - 19 Feb 2021
Viewed by 652
Abstract
One of the major aspects and advantages of solar energy conversion is the photocatalytic hydrogen generation using semiconductor materials for an eco-friendly technology. Designing a low-cost efficient material to overcome limited light absorption as well as rapid recombination of photogenerated charge carriers is [...] Read more.
One of the major aspects and advantages of solar energy conversion is the photocatalytic hydrogen generation using semiconductor materials for an eco-friendly technology. Designing a low-cost efficient material to overcome limited light absorption as well as rapid recombination of photogenerated charge carriers is essential to achieve considerable hydrogen generation. In recent years, sulfide based semiconductors have attracted scientific research interest due to their excellent solar response and narrow band gap. The present review focuses on the recent approaches in the development of hierarchical ternary sulfide based photocatalysts with a special focus on ZnIn2S4. We also observe how the electronic structure of ZnIn2S4 is beneficial for water splitting and the various strategies involved for improving the material efficiency for photocatalytic hydrogen generation. The review places emphasis on the latest advancement/new insights on ZnIn2S4 being used as an efficient material for hydrogen generation through photocatalytic water splitting. Recent progress on essential aspects which govern light absorption, charge separation and transport are also discussed in detail. Full article
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Open AccessArticle
Synthesis of Ethylene/1-Octene Copolymers with Ultrahigh Molecular Weights by Zr and Hf Complexes Bearing Bidentate NN Ligands with the Camphyl Linker
Catalysts 2021, 11(2), 276; https://doi.org/10.3390/catal11020276 - 18 Feb 2021
Viewed by 409
Abstract
Ultrahigh molecular weight polyethylene (UHMWPE) is a class of high-performance engineering plastics, exhibiting a unique set of properties and applications. Although many advances have been achieved in recent years, the synthesis of UHMWPE is still a great challenge. In this contribution, a series [...] Read more.
Ultrahigh molecular weight polyethylene (UHMWPE) is a class of high-performance engineering plastics, exhibiting a unique set of properties and applications. Although many advances have been achieved in recent years, the synthesis of UHMWPE is still a great challenge. In this contribution, a series of zirconium and hafnium complexes, [2,6-(R1)2-4-R2-C6H2-N-C(camphyl)=C(camphyl)-N-2,6-(R1)2-4-R2-C6H2]MMe2(THF) (1-Zr: R1 = Me, R2 = H, M = Zr; 2-Zr: R1 = Me, R2 = Me, M = Zr; 1-Hf: R1 = Me, R2 = H, M = Hf; 2-Hf: R1 = Me, R2 = Me, M = Hf), bearing bidentate NN ligands with the bulky camphyl backbone were synthesized by the stoichiometric reactions of α-diimine ligands with MMe4 (M = Hf or Zr). All Zr and Hf metal complexes were analyzed using 1H and 13C NMR spectroscopy, and the molecular structures of complexes 1-Zr and 1-Hf were determined by single-crystal X-ray diffraction, revealing that the original α-diimine ligand was selectively reduced into the ene-diamido form and generated an 1,3-diaza-2-metallocyclopentene ring in the metal complexes. Zr complexes 1-Zr and 2-Zr showed moderate activity (up to 388 kg(PE)·mol−1(M)·h−1), poor copolymerization ability, but unprecedented molecular weight capability toward ethylene/1-octene copolymerization. Therefore, copolymers with ultrahigh molecular weights (>600 or 337 × 104 g∙mol−1) were successfully synthesized by 1-Zr or 2-Zr, respectively, with the borate cocatalyst [Ph3C][B(C6F5)4]. Surprisingly, Hf complexes 1-Hf and 2-Hf showed negligible activity under otherwise identical conditions, revealing the great influence of metal centers on catalytic performances. Full article
(This article belongs to the Special Issue Catalysis in Plastics for the 21st Century)
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Open AccessReview
Advances in Homogeneous Photocatalytic Organic Synthesis with Colloidal Quantum Dots
Catalysts 2021, 11(2), 275; https://doi.org/10.3390/catal11020275 - 18 Feb 2021
Viewed by 472
Abstract
Colloidal semiconductor quantum dots (QDs) have been proven to be excellent photocatalysts due to their high photostability, large extinction coefficients, and tunable optoelectrical properties, and have attracted extensive attention by synthetic chemists. These excellent properties demonstrate its promise in the field of photocatalysis. [...] Read more.
Colloidal semiconductor quantum dots (QDs) have been proven to be excellent photocatalysts due to their high photostability, large extinction coefficients, and tunable optoelectrical properties, and have attracted extensive attention by synthetic chemists. These excellent properties demonstrate its promise in the field of photocatalysis. In this review, we summarize the recent application of QDs as homogeneous catalysts in various photocatalytic organic reactions. These meaningful works in organic transformations show the unique catalytic activity of quantum dots, which are different from other semiconductors. Full article
(This article belongs to the Special Issue Recent Advances in Photoredox Catalysts)
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Open AccessArticle
Biogas Reforming over Al-Co Catalyst Prepared by Solution Combustion Synthesis Method
Catalysts 2021, 11(2), 274; https://doi.org/10.3390/catal11020274 - 18 Feb 2021
Viewed by 510
Abstract
The results of carbon dioxide reforming of CH4 (model biogas) on catalysts prepared by solution combustion synthesis (SCS) and impregnation of moisture capacity methods are presented. Investigation of the activity of catalysts synthesized from initial mixtures of Co(NO3)2-Al(NO [...] Read more.
The results of carbon dioxide reforming of CH4 (model biogas) on catalysts prepared by solution combustion synthesis (SCS) and impregnation of moisture capacity methods are presented. Investigation of the activity of catalysts synthesized from initial mixtures of Co(NO3)2-Al(NO3)3-urea of different compositions was carried out for the production of synthesis-gas, and SCS and traditional incipient wetness impregnation catalyst preparation methods were compared. The methane conversion reached 100%, and the conversion of CO2 increased to 86.2%, while the yield of H2 and CO was 99.2% and 85.4%, respectively, at 900 °C. It was found that CoAl2O4 spinel formation was due to substitution of Al3+ with Co2+ cations. Consequently, CoAl2O4 lattice parameters increased, since the ionic radius of Al3+ (0.51 Å) less than Cο2+ (0.72 Å). Advantages of SCS catalysts in comparison with catalysts prepared by the traditional incipient wetness impregnation method in dry reforming of methane were shown. The aim of this work is to develop a new catalyst for the conversion of model biogas into synthesis gas, which will contribute to the organization of a new environmentally friendly, energy-saving production in the future. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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Open AccessArticle
A Novel Synthesizing Strategy of 3D Cose2 Porous Hollow Flowers for High Performance Lithium–Sulfur Batteries
Catalysts 2021, 11(2), 273; https://doi.org/10.3390/catal11020273 - 18 Feb 2021
Viewed by 387
Abstract
Redox kinetics of lithium polysulfides (LiPSs) conversion and poor electrical conductivity of sulfur during the charge-discharge process greatly inhibit the commercialization of high-performance lithium–sulfur (Li–S) batteries. Herein, we synthesized CoSe2 porous hollow flowers (CoSe2-PHF) by etching and further selenizing layered [...] Read more.
Redox kinetics of lithium polysulfides (LiPSs) conversion and poor electrical conductivity of sulfur during the charge-discharge process greatly inhibit the commercialization of high-performance lithium–sulfur (Li–S) batteries. Herein, we synthesized CoSe2 porous hollow flowers (CoSe2-PHF) by etching and further selenizing layered double hydroxide, which combined the high catalytic activity of transition metal compound and high electrical conductivity of selenium. The obtained CoSe2-PHF can efficiently accelerate the catalytic conversion of LiPSs, expedite the electron transport, and improve utilization of active sulfur during the charge-discharge process. As a result, with CoSe2-PHF/S-based cathodes, the Li–S batteries exhibited a reversible specific capacity of 955.8 mAh g−1 at 0.1 C and 766.0 mAh g−1 at 0.5 C, along with a relatively small capacity decay rate of 0.070% per cycle within 400 cycles at 1 C. Even at the high rate of 3 C, the specific capacity of 542.9 mAh g−1can be maintained. This work enriches the way to prepare porous composites with high catalytic activity and electrical conductivity as sulfur hosts for high-rate, long-cycle rechargeable Li–S batteries. Full article
(This article belongs to the Section Catalytic Materials)
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Open AccessEditorial
Progress in Catalytic Hydrodechlorination
Catalysts 2021, 11(2), 272; https://doi.org/10.3390/catal11020272 - 18 Feb 2021
Viewed by 367
Abstract
Catalytic hydrodechlorination (HDC) is a technology with great potential for the treatment and valorization of organic chlorinated wastes [...] Full article
(This article belongs to the Special Issue Progress in Catalytic Hydrodechlorination)
Open AccessFeature PaperArticle
Elucidating the Influence of Electric Fields toward CO2 Activation on YSZ (111)
Catalysts 2021, 11(2), 271; https://doi.org/10.3390/catal11020271 - 18 Feb 2021
Viewed by 651
Abstract
Despite its high thermodynamic stability, the presence of a negative electric field is known to facilitate the activation of CO2 through electrostatic effects. To utilize electric fields for a reverse water gas shift reaction, it is critical to elucidate the role of [...] Read more.
Despite its high thermodynamic stability, the presence of a negative electric field is known to facilitate the activation of CO2 through electrostatic effects. To utilize electric fields for a reverse water gas shift reaction, it is critical to elucidate the role of an electric field on a catalyst surface toward activating a CO2 molecule. We conduct a first-principles study to gain an atomic and electronic description of adsorbed CO2 on YSZ (111) surfaces when external electric fields of +1 V/Å, 0 V/Å, and −1 V/Å are applied. We find that the application of an external electric field generally destabilizes oxide bonds, where the direction of the field affects the location of the most favorable oxygen vacancy. The direction of the field also drastically impacts how CO2 adsorbs on the surface. CO2 is bound by physisorption when a +1 V/Å field is applied, a similar interaction as to how it is adsorbed in the absence of a field. This interaction changes to chemisorption when the surface is exposed to a −1 V/Å field value, resulting in the formation of a CO3 complex. The strong interaction is reflected through a direct charge transfer and an orbital splitting within the Olatticep-states. While CO2 remains physisorbed when a +1 V/Å field value is applied, our total density of states analysis indicates that a positive field pulls the charge away from the adsorbate, resulting in a shift of its bonding and antibonding peaks to higher energies, allowing a stronger interaction with YSZ (111). Ultimately, the effect of an electric field toward CO2 adsorption is not negligible, and there is potential in utilizing electric fields to favor the thermodynamics of CO2 reduction on heterogeneous catalysts. Full article
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Open AccessArticle
Kraft Lignin Ethanolysis over Zeolites with Different Acidity and Pore Structures for Aromatics Production
Catalysts 2021, 11(2), 270; https://doi.org/10.3390/catal11020270 - 18 Feb 2021
Viewed by 372
Abstract
To utilize its rich aromatics, lignin, a high-volume waste and environmental hazard, was depolymerized in supercritical ethanol over various zeolites types with different acidity and pore structures. Targeting at high yield/selectivity of aromatics such as phenols, microporous Beta, Y, and ZSM-5 zeolites were [...] Read more.
To utilize its rich aromatics, lignin, a high-volume waste and environmental hazard, was depolymerized in supercritical ethanol over various zeolites types with different acidity and pore structures. Targeting at high yield/selectivity of aromatics such as phenols, microporous Beta, Y, and ZSM-5 zeolites were first examined in lignin ethanolysis, followed by zeolites with similar micropore size but different acidity. Further comparisons were made between zeolites with fin-like and worm-like mesoporous structures and their microporous counterparts. Despite depolymerization complexity and diversified ethanolysis products, strong acidity was found effective to cleave both C–O–C and C–C linkages of lignin while mild acidity works mainly in ether bond breakdown. However, when diffusion of gigantic molecules is severe, pore size, particularly mesopores, becomes more decisive on phenol selectivity. These findings provide important guidelines on future selection and design of zeolites with appropriate acidity and pore structure to promote lignin ethanolysis or other hydrocarbon cracking processes. Full article
(This article belongs to the Special Issue Catalytic Conversion of Lignins for Valuable Chemicals)
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Open AccessArticle
Fed-Batch Cultivation and Adding Supplements to Increase Yield of β-1,3-1,4-Glucanase by Genetically Engineered Escherichia coli
Catalysts 2021, 11(2), 269; https://doi.org/10.3390/catal11020269 - 18 Feb 2021
Viewed by 405
Abstract
The aim of this study was to analyze the major influence factors of culture medium on the expression level of β-1,3-1,4-glucanase, and to further develop an optimized process for the extracellular production of β-glucanase at a bioreactor scale (7 L) with a genetically [...] Read more.
The aim of this study was to analyze the major influence factors of culture medium on the expression level of β-1,3-1,4-glucanase, and to further develop an optimized process for the extracellular production of β-glucanase at a bioreactor scale (7 L) with a genetically engineered Escherichia coli (E. coli) JM109-pLF3. In this study, batch cultivation and fed-batch cultivation including the constant rate feeding strategy and the DO-stat (DO: Dissolved Oxygen) feeding strategy were conducted. At a 7 L bioreactor scale for batch cultivation, biomass reached 3.14 g/L and the maximum β-glucanase activity was 506.94 U/mL. Compared with batch cultivation, the addition of glycerol, complex nitrogen and complete medium during fed-batch cultivation increased the production of biomass and β-1,3-1,4-glucanase. The maximum biomass and β-glucanase activity, which were 7.67 g/L and 1680 U/mL, respectively, that is, 2.45 and 3.31 times higher than those obtained with batch cultivation, were obtained by feeding a complex nitrogen source at a constant rate of 1.11 mL/min. Therefore, these nutritional supplements and strategies can be used as a reference to enhance the production of other bioproducts from E. coli. Full article
(This article belongs to the Special Issue Recent Advances in Biocatalysis and Metabolic Engineering)
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Open AccessReview
Recent Advances in Applications of Co-B Catalysts in NaBH4-Based Portable Hydrogen Generators
Catalysts 2021, 11(2), 268; https://doi.org/10.3390/catal11020268 - 17 Feb 2021
Viewed by 442
Abstract
This review highlights the opportunities of catalytic hydrolysis of NaBH4 with the use of inexpensive and active Co-B catalysts among the other systems of hydrogen storage and generation based on water reactive materials. This process is important for the creation of H [...] Read more.
This review highlights the opportunities of catalytic hydrolysis of NaBH4 with the use of inexpensive and active Co-B catalysts among the other systems of hydrogen storage and generation based on water reactive materials. This process is important for the creation of H2 generators required for the operation of portable compact power devices based on low-temperature proton exchange membrane fuel cells (LT PEM FC). Special attention is paid to the influence of the reaction medium on the formation of active state of Co-B catalysts and the problem of their deactivation in NaBH4 solution stabilized by alkali. The novelty of this review consists in the discussion of basic designs of hydrogen generators based on NaBH4 hydrolysis using cobalt catalysts and the challenges of their integration with LT PEM FC. The potential of using batch reactors in which there is no need to use aggressive alkaline NaBH4 solutions is discussed. Solid-phase compositions or pellets based on NaBH4 and cobalt-containing catalytic additives are proposed, the hydrogen generation from which starts immediately after the addition of water. The review made it possible to formulate the most acute problems, which require new sci-tech solutions. Full article
(This article belongs to the Special Issue Cobalt Catalysis: Recent Progress and Developments)
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Open AccessArticle
Regioselective Hydroxylation of Oleanolic Acid Catalyzed by Human CYP3A4 to Produce Hederagenenin, a Chiral Metabolite
Catalysts 2021, 11(2), 267; https://doi.org/10.3390/catal11020267 - 17 Feb 2021
Viewed by 393
Abstract
Oleanolic acid (OA) is a pentacyclic triterpenoid widely found in plants and foods as an aglycone of triterpenoid saponins or as a free acid. OA exhibits beneficial activities for humans, including antitumor, antivirus, and hepatoprotection properties without apparent toxicity. The metabolites produced by [...] Read more.
Oleanolic acid (OA) is a pentacyclic triterpenoid widely found in plants and foods as an aglycone of triterpenoid saponins or as a free acid. OA exhibits beneficial activities for humans, including antitumor, antivirus, and hepatoprotection properties without apparent toxicity. The metabolites produced by the cytochrome P450 (P450) enzymes are critical for the evaluation of the efficacy and safety of drugs. In this study, the potential metabolites of OA were investigated by P450-catalyzed oxidation reactions. Among the various tested human P450s, only human CYP3A4 was active for the hydroxylation of OA. The major metabolite was characterized by a set of analyses using HPLC, LC–MS, and NMR. It was found to be 4-epi-hederagenenin, a chiral product, by regioselective hydroxylation of the methyl group at the C-23 position. These results indicated that CYP3A4 can hydroxylate an OA substrate to make 4-epi-hederagenenin. Possible drug–food interactions are discussed. Full article
(This article belongs to the Special Issue Recent Advances in Biocatalysis and Metabolic Engineering)
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Open AccessFeature PaperReview
Intensification of Chemical Looping Processes by Catalyst Assistance and Combination
Catalysts 2021, 11(2), 266; https://doi.org/10.3390/catal11020266 - 17 Feb 2021
Viewed by 498
Abstract
Chemical looping can be considered a technology platform, which refers to one common basic concept that can be used for various applications. Compared with a traditional catalytic process, the chemical looping concept allows fuels’ conversion and products’ separation without extra processes. In addition, [...] Read more.
Chemical looping can be considered a technology platform, which refers to one common basic concept that can be used for various applications. Compared with a traditional catalytic process, the chemical looping concept allows fuels’ conversion and products’ separation without extra processes. In addition, the chemical looping technology has another major advantage: combinability, which enables the integration of different reactions into one process, leading to intensification. This review collects various important state-of-the-art examples, such as integration of chemical looping and catalytic processes. Hereby, we demonstrate that chemical looping can in principle be implemented for any catalytic reaction or at least assist in existing processes, provided that the targeted functional group is transferrable by means of suitable carriers. Full article
(This article belongs to the Special Issue Chemical Looping for Catalysis)
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Open AccessFeature PaperReview
Catalyst Stability—Bottleneck of Efficient Catalytic Pyrolysis
Catalysts 2021, 11(2), 265; https://doi.org/10.3390/catal11020265 - 16 Feb 2021
Viewed by 474
Abstract
The pyrolysis of lignocellulosic biomass is one of the most promising methods of alternative fuels production. However, due to the low selectivity of this process, the quality of the obtained bio-oil is usually not satisfactory and does not allow for its direct use [...] Read more.
The pyrolysis of lignocellulosic biomass is one of the most promising methods of alternative fuels production. However, due to the low selectivity of this process, the quality of the obtained bio-oil is usually not satisfactory and does not allow for its direct use as an engine fuel. Therefore, there is a need to apply catalysts able to upgrade the composition of the mixture of pyrolysis products. Unfortunately, despite the increase in the efficiency of the thermal decomposition of biomass, the catalysts undergo relatively fast deactivation and their stability can be considered a bottleneck of efficient pyrolysis of lignocellulosic feedstock. Therefore, solving the problem of catalyst stability is extremely important. Taking that into account, we presented, in this review, the most important reasons for catalyst deactivation, including coke formation, sintering, hydrothermal instability, and catalyst poisoning. Moreover, we discussed the progress in the development of methods leading to an increase in the stability of the catalysts of lignocellulosic biomass pyrolysis and strengthening their resistance to deactivation. Full article
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