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Catalysts, Volume 9, Issue 4 (April 2019)

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Cover Story (view full-size image) In this paper (Catalysts 2019, 9, 321), Kirillov and co-workers report a self-assembly synthesis, [...] Read more.
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Open AccessArticle
Efficient Biocatalytic Preparation of Optically Pure (R)-1-[4-(Trifluoromethyl)phenyl]ethanol by Recombinant Whole-Cell-Mediated Reduction
Catalysts 2019, 9(4), 391; https://doi.org/10.3390/catal9040391
Received: 31 March 2019 / Revised: 17 April 2019 / Accepted: 19 April 2019 / Published: 25 April 2019
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Abstract
(R)-1-[4-(Trifluoromethyl)phenyl]ethanol is an important pharmaceutical intermediate of a chemokine CCR5 antagonist. In the present study, a bioprocess for the asymmetric reduction of 4-(trifluoromethyl)acetophenone to (R)-1-[4-(trifluoromethyl)phenyl]ethanol was developed by recombinant Escherichia coli cells with excellent enantioselectivity. In order to overcome [...] Read more.
(R)-1-[4-(Trifluoromethyl)phenyl]ethanol is an important pharmaceutical intermediate of a chemokine CCR5 antagonist. In the present study, a bioprocess for the asymmetric reduction of 4-(trifluoromethyl)acetophenone to (R)-1-[4-(trifluoromethyl)phenyl]ethanol was developed by recombinant Escherichia coli cells with excellent enantioselectivity. In order to overcome the conversion limitation performed in the conventional buffer medium resulting from poor solubility of non-natural substrate, we subsequently established a polar organic solvent-aqueous medium to improve the efficacy. Isopropanol was selected as the most suitable cosolvent candidate, based on the investigation on a substrate solubility test and cell membrane permeability assay in different organic solvent-buffer media. Under the optimum conditions, the preparative-scale asymmetric reduction generated a 99.1% yield with >99.9% product enantiomeric excess (ee) in a 15% (v/v) isopropanol proportion, at 100 mM of 4-(trifluoromethyl)acetophenone within 3 h. Compared to bioconversion in the buffer medium, the developed isopropanol-aqueous system enhanced the substrate concentration by 2-fold with a remarkably improved yield (from 62.5% to 99.1%), and shortened the reaction time by 21 h. Our study gave the first example for a highly enantioselective production of (R)-1-[4-(trifluoromethyl)phenyl]ethanol by a biological method, and the bioreduction of 4-(trifluoromethyl)acetophenone in a polar organic solvent-aqueous system was more efficient than that in the buffer solution only. This process is also scalable and has potential in application. Full article
(This article belongs to the Special Issue Biocatalysts: Design and Application)
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Open AccessArticle
Hierarchically-Structured TiO2/MnO2 Hollow Spheres Exhibiting the Complete Mineralization of Phenol
Catalysts 2019, 9(4), 390; https://doi.org/10.3390/catal9040390
Received: 19 March 2019 / Revised: 8 April 2019 / Accepted: 13 April 2019 / Published: 25 April 2019
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Abstract
Although TiO2 or MnO2-based materials have been widely used for the degradation of phenolic compounds, complete mineralization is still a challenge, especially for TiO2-based materials. Here, we devise a hierarchically-structured TiO2/MnO2 (HTM) hollow sphere, in [...] Read more.
Although TiO2 or MnO2-based materials have been widely used for the degradation of phenolic compounds, complete mineralization is still a challenge, especially for TiO2-based materials. Here, we devise a hierarchically-structured TiO2/MnO2 (HTM) hollow sphere, in which hollow TiO2 acts as a skeleton for the deposition of MnO2 in order to prevent the aggregation of MnO2 nanoparticles and to maintain its hollow structure. During the oxidation reaction, the as-synthesized HTM can fully exert their respective advantages of the TiO2 and MnO2 species to realize the first stage of the rapid oxidation degradation of phenol and the second stage of the complete photo-mineralization of residual phenol and its intermediates, which efficiently overcomes the incomplete mineralization of phenolic compounds. The degradation mechanism and pathway of phenol are also proposed according to the analysis of Mass Spectrometry (MS). Therefore, this work provides a new insight for exploring hierarchically-structured materials with two or more species. Full article
(This article belongs to the Special Issue Nanostructured Materials for Photocatalysis)
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Open AccessArticle
Solar-Driven Removal of 1,4-Dioxane Using WO3/nγ-Al2O3 Nano-catalyst in Water
Catalysts 2019, 9(4), 389; https://doi.org/10.3390/catal9040389
Received: 5 April 2019 / Revised: 22 April 2019 / Accepted: 24 April 2019 / Published: 25 April 2019
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Abstract
Increasing demand for fresh water in extreme drought regions necessitates potable water reuse. However, current membrane-based water reclamation approaches cannot effectively remove carcinogenic 1,4-dioxane. The current study reports on the solar-driven removal of 1,4-dioxane (50 mg L−1) using a homemade WO [...] Read more.
Increasing demand for fresh water in extreme drought regions necessitates potable water reuse. However, current membrane-based water reclamation approaches cannot effectively remove carcinogenic 1,4-dioxane. The current study reports on the solar-driven removal of 1,4-dioxane (50 mg L−1) using a homemade WO3/nγ-Al2O3 nano-catalyst. Characterization methods including scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF) analyses are used to investigate the surface features of the catalyst. The 1,4-dioxane mineralization performance of this catalyst under various reaction conditions is studied. The effect of the catalyst dosage is tested. The mean oxidation state carbon (MOSC) values of the 1,4-dioxane solution are followed during the reaction. The short chain organic acids after treatment are measured. The results showed that over 75% total organic carbon (TOC) removal was achieved in the presence of 300 mg L−1 of the catalyst with a simulated solar irradiation intensity of 40 mW cm−2. Increasing the dose of the catalyst from 100 to 700 mg L−1 can improve the treatment efficiency to some extent. The TOC reduction curve fits well with an apparent zero-order kinetic model and the corresponding constant rates are within 0.0927 and 0.1059 mg L−1 s−1, respectively. The MOSC values of the 1,4-dioxane solution increase from 1.3 to 3 along the reaction, which is associated with the formation of some short chain acids. The catalyst can be effectively reused 7 times. This work provides an oxidant-free and energy saving approach to achieve efficient removal of 1,4-dioxane and thus shows promising potential for potable reuse applications. Full article
(This article belongs to the Special Issue Trends in Catalytic Wet Peroxide Oxidation Processes)
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Open AccessArticle
Synthesis of the First Resorcin[4]arene-Functionalized Triazolium Salts and Their Use in Suzuki–Miyaura Cross-Coupling Reactions
Catalysts 2019, 9(4), 388; https://doi.org/10.3390/catal9040388
Received: 18 March 2019 / Revised: 12 April 2019 / Accepted: 23 April 2019 / Published: 25 April 2019
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Abstract
Two bulky triazolium salts, namely 1-{4(24),6(10),12(16),18(22)-tetramethylenedioxy- 2,8,14,20-tetrapentylresorcin[4]arene-5-yl}-4-phenyl-3-methyl-1H-1,2,3-triazolium tetrafluoro borate (1) and 1,4-bis{4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentyl resorcin[4]arene-5-yl}-3-methyl-1H-1,2,3-triazolium iodide (2), have been synthesized and assessed in the palladium-catalyzed Suzuki–Miyaura cross-coupling of aryl chlorides, with aryl boronic acids. As a general [...] Read more.
Two bulky triazolium salts, namely 1-{4(24),6(10),12(16),18(22)-tetramethylenedioxy- 2,8,14,20-tetrapentylresorcin[4]arene-5-yl}-4-phenyl-3-methyl-1H-1,2,3-triazolium tetrafluoro borate (1) and 1,4-bis{4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentyl resorcin[4]arene-5-yl}-3-methyl-1H-1,2,3-triazolium iodide (2), have been synthesized and assessed in the palladium-catalyzed Suzuki–Miyaura cross-coupling of aryl chlorides, with aryl boronic acids. As a general trend, the reaction rates obtained with 1 were significantly higher (up to 5 times) than those observed for 2, this mainly reflected a sterically more accessible metal center in the catalytic intermediates formed with 1. The presence of flexible pentyl chains in these intermediates, which might sterically interact with the metal center, when the latter adopts an exo-orientation with respect to the cavity, were likely responsible for the observed good performance. Full article
(This article belongs to the Special Issue Catalysts for Suzuki–Miyaura Coupling Reaction)
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Open AccessArticle
Electrocatalytic Oxidation of Small Molecule Alcohols over Pt, Pd, and Au Catalysts: The Effect of Alcohol’s Hydrogen Bond Donation Ability and Molecular Structure Properties
Catalysts 2019, 9(4), 387; https://doi.org/10.3390/catal9040387
Received: 1 March 2019 / Revised: 15 April 2019 / Accepted: 16 April 2019 / Published: 25 April 2019
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Abstract
The direct alcohol fuel cell is a kind of power generation device that directly converts the chemical energy of small molecule alcohols into electric energy. In this paper, the electro-oxidation behaviors of some typical alcohols (methanol, ethanol, ethylene glycol, n-propanol, 2-propanol, and glycerol) [...] Read more.
The direct alcohol fuel cell is a kind of power generation device that directly converts the chemical energy of small molecule alcohols into electric energy. In this paper, the electro-oxidation behaviors of some typical alcohols (methanol, ethanol, ethylene glycol, n-propanol, 2-propanol, and glycerol) over Pt, Pd, and Au electrodes were investigated in acidic, neutral, and alkaline media, respectively. By analyzing the activity information from a cyclic voltammetry (CV) method and some dynamic tests, several regularities were revealed in those electro-oxidation behaviors. Firstly, alkaline media is the best for the electro-oxidation of all these alcohols over Pt, Pd, and Au catalysts. Secondly, the hydrogen bond donation abilities (HBD) of different alcohols were found have a great relationship with the catalytic performance. In alkaline media, on Pt electrodes, the solute HBD is positively correlated with the ease of electrooxidation within the scope of this experiment. Contrarily, it is negatively correlated on Pd and Au electrodes. Additionally, for Pt catalysts in acidic and neutral media, the relationship becomes negative again as the HBD increases. Finally, the alcohol’s molecular structure properties were found to have a remarkably influence on the activity of different catalysts. Over the Pt electrode in alkaline media, the activation energy of methanol oxidation is 44.1 KJ/mol, and is obviously lower than the oxidation of other alcohols. Under similar conditions, the lowest activation energy was measured in the oxidation of n-propanol (14.4 KJ/mol) over the Pd electrode, and in the oxidation of glycerol (42.2 KJ/mol) over the Au electrode. Totally, among all these electrodes, Pt electrodes showed the best activities on the oxidation of C1 alcohol, Pd electrodes were more active on the oxidation of C2-3 monobasic alcohols, and Au electrodes were more active on the oxidation of polybasic alcohols. Full article
(This article belongs to the Special Issue Catalysis for Electro-oxidation of Ethanol & Methanol)
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Open AccessArticle
Point-Defect-Rich Carbon Sheets as the High-Activity Catalyst Toward Oxygen Reduction and Hydrogen Evolution
Catalysts 2019, 9(4), 386; https://doi.org/10.3390/catal9040386
Received: 17 March 2019 / Revised: 8 April 2019 / Accepted: 18 April 2019 / Published: 25 April 2019
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Abstract
Exploring a novel approach for the synthesis of oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) catalysts with inexpensive and high-activity is desirable. Herein, we report a bubble templating method to synthesize the graphene-like mesoporous carbon sheets with point defects as ORR/HER [...] Read more.
Exploring a novel approach for the synthesis of oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) catalysts with inexpensive and high-activity is desirable. Herein, we report a bubble templating method to synthesize the graphene-like mesoporous carbon sheets with point defects as ORR/HER bifunctional electrocatalysts. The typical product shows excellent ORR performance including the positive onset potential (740 mV) and high diffusion-limiting current density (4.07 mA cm−2). Along with small Tafel slopes, the overpotential is determined to be about −453 and −378 mV at 10 mA cm−2 in both alkaline and acidic media, which suggests a good candidate for HER reaction as well. The superior catalytic activities are derived from the abundant point defects on the mesoporous carbon sheets surface, especially the existence of pyridinic and pyrrolic nitrogen species. This study may be an alternative route to prepare the novel functional materials for the applications of ORR and HER. Full article
(This article belongs to the Special Issue Electro-Catalysts for Energy Conversion and Storage Devices)
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Open AccessCommunication
Ultra-Small Pd Nanoparticles on Ceria as an Advanced Catalyst for CO Oxidation
Catalysts 2019, 9(4), 385; https://doi.org/10.3390/catal9040385
Received: 7 March 2019 / Revised: 16 April 2019 / Accepted: 21 April 2019 / Published: 24 April 2019
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Abstract
In this study, we demonstrate the preparation and characterization of small palladium nanoparticles (Pd NPs) on modified ceria support (Pd/CeO2) using wet impregnation and further reduction in an H2/Ar flow. The obtained particles had a good dispersion, but their [...] Read more.
In this study, we demonstrate the preparation and characterization of small palladium nanoparticles (Pd NPs) on modified ceria support (Pd/CeO2) using wet impregnation and further reduction in an H2/Ar flow. The obtained particles had a good dispersion, but their small size made it difficult to analyze them by conventional techniques such as transmission electron microscopy (TEM) and X-ray powder diffraction (XRPD). The material demonstrated a high catalytic activity in the CO oxidation reaction: the 100% of CO conversion was achieved at ~50 °C, whereas for most of the cited literature, such a high conversion usually was observed near 100 °C or higher for Pd NPs. Diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy in combination with CO probe molecules was used to investigate the size and morphology of NPs and the ceria support. On the basis of the area ratio under the peaks attributed to bridged (B) and linear (L) carbonyls, high-dispersion Pd NPs was corroborated. Obtained results were in good agreement with data of X-ray absorption near edge structure analysis (XANES) and CO chemisorption measurements. Full article
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Open AccessArticle
Hydroconversion of Aromatic Hydrocarbons over Bimetallic Catalysts
Catalysts 2019, 9(4), 384; https://doi.org/10.3390/catal9040384
Received: 9 March 2019 / Revised: 15 April 2019 / Accepted: 22 April 2019 / Published: 24 April 2019
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Abstract
Bimetallic catalysts (BMC) for hydroconversion of aromatic hydrocarbons (ArH) have been designed by modification of Ni/Al2O3 with chromium(0) compounds and phosphoromolybdic heteropolyacid (HPA). Catalysts were tested in hydrogenation of benzene and toluene, in hydrodemethylation of pure toluene and they were [...] Read more.
Bimetallic catalysts (BMC) for hydroconversion of aromatic hydrocarbons (ArH) have been designed by modification of Ni/Al2O3 with chromium(0) compounds and phosphoromolybdic heteropolyacid (HPA). Catalysts were tested in hydrogenation of benzene and toluene, in hydrodemethylation of pure toluene and they were shown to possess a high activity, selectivity and sulfur tolerance under conditions of the processes above. The activity of BMC in these processes was much higher as compared with that of two-component (Ni-Cr, Ni-HPA) or conventional Ni/Al2O3 catalysts. Using BMC, hydrogenation of benzene and toluene proceeds with activity increased (up to 34–38 mol/kg·h) and toluene hydrodemethylation may be performed with improved selectivity (90.3%) and benzene yield (81%). The high sulfur tolerance of BMC was demonstrated by performing hydrodemethylation of toluene containing up to 500 ppm S. Full article
(This article belongs to the Special Issue Catalytic Applications of Bimetallic Nanoparticles)
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Open AccessArticle
Formation of CuO on TiO2 Surface Using its Photocatalytic Activity
Catalysts 2019, 9(4), 383; https://doi.org/10.3390/catal9040383
Received: 3 April 2019 / Accepted: 22 April 2019 / Published: 24 April 2019
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Abstract
Some co-catalyst nanoparticles can enhance the activity of photocatalysts due to prolonging the charge separation lifetime by promoting the electron or hole transfer. CuO particles were prepared from an aqueous solution of copper (II) nitrate at 351 K on a TiO2 surface [...] Read more.
Some co-catalyst nanoparticles can enhance the activity of photocatalysts due to prolonging the charge separation lifetime by promoting the electron or hole transfer. CuO particles were prepared from an aqueous solution of copper (II) nitrate at 351 K on a TiO2 surface by a photocatalytic reaction and heating at 573 or 673 K. The amount and size of the particles deposited during the photocatalytic reaction can be controlled by changing the amount of the irradiated photons. The CuO crystals with about 50−250 nm-sized particles were formed. Nitrate ions were reduced to nitrite ions in the solution by the photocatalytic activity of the TiO2, and water was simultaneously transformed into hydroxide ions. An increase in the basicity on the TiO2 surface induced formation of a copper hydroxide. The copper hydroxide was subsequently dehydrated and transformed into CuO by heating. The TiO2 loading of a small amount of CuO demonstrated a higher photocatalytic activity for methylene blue degradation compared to the original TiO2 due to the electron transfer from the TiO2 conduction bands to the CuO conduction band. Full article
(This article belongs to the Section Photocatalysis)
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Open AccessArticle
Mechanically-Induced Catalyzation of MgH2 Powders with Zr2Ni-Ball Milling Media
Catalysts 2019, 9(4), 382; https://doi.org/10.3390/catal9040382
Received: 15 April 2019 / Revised: 20 April 2019 / Accepted: 22 April 2019 / Published: 24 April 2019
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Abstract
Magnesium hydride (MgH2) holds immense promises as a cost-effective hydrogen storage material that shows excellent storage capacity suitable for fuel cell applications. Due to its slow hydrogen charging/discharging kinetics and high apparent activation energy of decomposition, MgH2 is usually doped [...] Read more.
Magnesium hydride (MgH2) holds immense promises as a cost-effective hydrogen storage material that shows excellent storage capacity suitable for fuel cell applications. Due to its slow hydrogen charging/discharging kinetics and high apparent activation energy of decomposition, MgH2 is usually doped with one or more catalytic agents to improve its storage capacity. So often, milling the metal hydride with proper amounts of catalyst leads to heterogeneous distribution of the catalytic agent(s) in MgH2 matrix. The present work proposes a cost-effective process for doping Mg powders with Zr2Ni particles upon ball milling the powders with Zr2Ni-balls milling media under pressurized hydrogen. Fine Zr2Ni particles were gradually eroded from the balls and homogeneously embedded into the milled powders upon increasing the ball milling time. As a result, these fine hard intermetallic particles acted as micro-milling media and leading to the reduction the Mg/MgH2 powders. Meanwhile, Zr2Ni eroded particles possessed excellent heterogeneous catalytic effect for improving the hydrogenation/dehydrogenation kinetics of MgH2. This is implied by the short time required to absorb (425 s)/desorb (700 s) 6.2 wt% H2 at 200 °C and 225 °C, respectively. The as-milled MgH2 with Zr2Ni balls possessed excellent cyclability, indexed by achieving continuous 646 cycles in 985.5 h (~1.5 cycle per hour) without serious degradation. Full article
(This article belongs to the Section Catalytic Materials)
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Open AccessFeature PaperArticle
Catalytic Properties of Double Substituted Lanthanum Cobaltite Nanostructured Coatings Prepared by Reactive Magnetron Sputtering
Catalysts 2019, 9(4), 381; https://doi.org/10.3390/catal9040381
Received: 29 March 2019 / Revised: 16 April 2019 / Accepted: 17 April 2019 / Published: 23 April 2019
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Abstract
Lanthanum perovskites are promising candidates to replace platinum group metal (PGM), especially regarding catalytic oxidation reactions. We have prepared thin catalytic coatings of Sr and Ag doped lanthanum perovskite by using the cathodic co-sputtering magnetron method in reactive condition. Such development of catalytic [...] Read more.
Lanthanum perovskites are promising candidates to replace platinum group metal (PGM), especially regarding catalytic oxidation reactions. We have prepared thin catalytic coatings of Sr and Ag doped lanthanum perovskite by using the cathodic co-sputtering magnetron method in reactive condition. Such development of catalytic films may optimize the surface/bulk ratio to save raw materials, since a porous coating can combine a large exchange surface with the gas phase with an extremely low loading. The sputtering deposition process was optimized to generate crystallized and thin perovskites films on alumina substrates. We found that high Ag contents has a strong impact on the morphology of the coatings. High Ag loadings favor the growth of covering films with a porous wire-like morphology showing a good catalytic activity for CO oxidation. The most active composition displays similar catalytic performances than those of a Pt film. In addition, this porous coating is also efficient for CO and NO oxidation in a simulated Diesel exhaust gas mixture, demonstrating the promising catalytic properties of such nanostructured thin sputtered perovskite films. Full article
(This article belongs to the Special Issue Emissions Control Catalysis)
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Open AccessArticle
Numerical Evaluation of Potential Catalyst Savings for Ventilation Air Methane Catalytic Combustion in Helical Coil Reactors with Selective Wall Coating
Catalysts 2019, 9(4), 380; https://doi.org/10.3390/catal9040380
Received: 25 March 2019 / Revised: 19 April 2019 / Accepted: 20 April 2019 / Published: 23 April 2019
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Abstract
During active mining operation of a gassy underground mine, large amounts of methane will be released from the mine ventilation shaft. To eliminate the harmful effects of this ventilation air methane and minimize the wastage of this potential energy resource, considerable effort has [...] Read more.
During active mining operation of a gassy underground mine, large amounts of methane will be released from the mine ventilation shaft. To eliminate the harmful effects of this ventilation air methane and minimize the wastage of this potential energy resource, considerable effort has been devoted to converting this alternative fuel using catalytic combustion. This study numerically investigated the reaction performance of ventilation air methane (VAM) in helical coil tubes of various configurations utilizing a computational fluid dynamics (CFDs) approach. Several key factors affecting the catalytic combustion performance such as curvature, inlet Reynolds number, and cross-section aspect ratio were evaluated. Recalling the high cost of the catalyst used in this reaction—platinum—optimization of catalyst usage by implementing selective catalyst coating was conducted and investigated. For evaluation purposes, the reaction performance of the helical coil tube was compared to its straight counterpart. The results gave a firm confirmation of the superior performance of the helical coil tube compared to the straight one. In addition, it was found that the selective inner wall coating in the circular cross-section at a higher Reynolds number gave rise to the highest figure of merit (FoM), defined as the net energy produced per mg of catalyst platinum. Full article
(This article belongs to the Special Issue Reactors and Models in Catalysis)
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Open AccessArticle
MoS2/CdS Heterostructure for Enhanced Photoelectrochemical Performance under Visible Light
Catalysts 2019, 9(4), 379; https://doi.org/10.3390/catal9040379
Received: 14 March 2019 / Revised: 19 April 2019 / Accepted: 22 April 2019 / Published: 23 April 2019
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Abstract
High-rate recombination of photogenerated electron and hole pairs will lead to low photocatalytic activity. Constructing heterostructure is a way to address this problem and thus increase the photoelectrochemical performance of the photocatalysts. In this article, molybdenum sulfide (MoS2)/cadmium sulfide (CdS) nanocomposites [...] Read more.
High-rate recombination of photogenerated electron and hole pairs will lead to low photocatalytic activity. Constructing heterostructure is a way to address this problem and thus increase the photoelectrochemical performance of the photocatalysts. In this article, molybdenum sulfide (MoS2)/cadmium sulfide (CdS) nanocomposites were fabricated by a facile solvothermal method after sonication. The CdS nanoparticles immobilized on the MoS2 sheet retained the original crystal structure and morphology. The composites exhibit higher photoelectrochemical properties compared with pure MoS2 nanosheets or CdS powder. When the precursor concentration of CdS is 0.015 M, the MoS2/CdS composites yield the highest photocurrent, which is enhanced nearly five times compared with pure CdS or MoS2. The improved photoelectrochemical performance can be ascribed to the increase of light harvest, as well as to the heterostructure that decreases the recombination rate of the photogenerated electron and hole pairs. Full article
(This article belongs to the Special Issue Photocatalytic Nanocomposite Materials)
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Open AccessArticle
Improved Etherification of Glycerol with Tert-Butyl Alcohol by the Addition of Dibutyl Ether as Solvent
Catalysts 2019, 9(4), 378; https://doi.org/10.3390/catal9040378
Received: 26 March 2019 / Revised: 12 April 2019 / Accepted: 17 April 2019 / Published: 23 April 2019
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Abstract
The etherification of glycerol with tert-butyl alcohol in the presence of acid catalysts gives rise to the production of ethers (monoethers, diethers and triethers) of high added-value, which can be used as oxygenated additives in fuels. This reaction is limited by the [...] Read more.
The etherification of glycerol with tert-butyl alcohol in the presence of acid catalysts gives rise to the production of ethers (monoethers, diethers and triethers) of high added-value, which can be used as oxygenated additives in fuels. This reaction is limited by the thermodynamic equilibrium, which can be modified by the addition of solvents that selectively solubilize the products of interest along with tert-butyl alcohol, leading to the progress of the reaction. In this work, it has been demonstrated that the addition of dibutyl ether allows shifting the reaction equilibrium, increasing the production of diethers. From the study of the main operating conditions, it was determined that an increase in the concentration of the solvent has a positive effect on the selectivity towards the production of diethers, the concentration of the catalyst (a commercial ion exchange resin, Amberlyst 15, named A-15) and the reaction temperature were also determining variables. Working with concentrations of tert-butyl alcohol above the stoichiometric one did not report great advantages. The optimal operating conditions to maximize the conversion of glycerol and the selectivity towards diethers were: 70 °C, 20% catalyst (referred to the total starting mass of the system), the stoichiometric ratio of glycerol:tert-butyl alcohol (G:TB = 1:3) and 1:2 molar ratio of dibutyl ether:tert-butyl alcohol. A study of three consecutive reaction cycles showed the high stability of the catalyst, obtaining identical results. Full article
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Open AccessArticle
Effect of Cerium Precursor in the Synthesis of Ce-MCM-41 and in the Efficiency for Liquid-Phase Oxidation of Benzyl Alcohol
Catalysts 2019, 9(4), 377; https://doi.org/10.3390/catal9040377
Received: 14 March 2019 / Revised: 4 April 2019 / Accepted: 17 April 2019 / Published: 23 April 2019
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Abstract
Understanding the effects of synthetic parameters in the catalytic activity of heterogeneous catalysts is of utmost importance when aiming for optimal reaction conditions. Hence, we disclose in this work the synthesis and characterization of cerium-modified MCM-41 materials. In addition, it was observed for [...] Read more.
Understanding the effects of synthetic parameters in the catalytic activity of heterogeneous catalysts is of utmost importance when aiming for optimal reaction conditions. Hence, we disclose in this work the synthesis and characterization of cerium-modified MCM-41 materials. In addition, it was observed for the first time, differences in catalytic activity when using different cerium synthetic precursors: CeCl3·7H2O and Ce(NO3)3·6H2O (Ce-MCM-Cl and Ce-MCM-NO3, respectively). A mechanism for cerium incorporation in MCM-41 was proposed, where [Ce(OH)3] species were hydrogen bonded to silicate anions, forming framework Ce-O-Si bonds during condensation and, consequently, causing distortion of the typical hexagonal mesophase. It was also observed that Ce(OH)3 formed aggregated layers with template assemblies during synthesis, resulting in non-framework CeO2 species on the MCM-41 surface after calcination. These CeO2 species were preferentially formed for Ce-MCM-NO3 and were attributed to the nitrate ions’ strong binding to template molecules. In the solvent free liquid-phase oxidation of benzyl alcohol (BzOH), Ce-MCM-Cl achieved better BzOH conversions and benzaldehyde (BzD) yields, while Ce-MCM-NO3 offered increased BzD selectivity. The catalysts’ reusability was also studied over three catalytic runs, where Ce-MCM-NO3 was more resistant than Ce-MCM-Cl towards deactivation. The observed catalytic behavior shows the importance of metal precursors in the obtainment of materials with desirable final properties. Full article
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Open AccessFeature PaperArticle
Hydrogen Production from Formic Acid over Au Catalysts Supported on Carbon: Comparison with Au Catalysts Supported on SiO2 and Al2O3
Catalysts 2019, 9(4), 376; https://doi.org/10.3390/catal9040376
Received: 28 March 2019 / Revised: 11 April 2019 / Accepted: 13 April 2019 / Published: 22 April 2019
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Abstract
Characteristics and catalytic activity in hydrogen production from formic acid of Au catalysts supported on porous N-free (Au/C) and N-doped carbon (Au/N-C) have been compared with those of Au/SiO2 and Au/Al2O3 catalysts. Among the catalysts examined, the Au/N-C catalyst [...] Read more.
Characteristics and catalytic activity in hydrogen production from formic acid of Au catalysts supported on porous N-free (Au/C) and N-doped carbon (Au/N-C) have been compared with those of Au/SiO2 and Au/Al2O3 catalysts. Among the catalysts examined, the Au/N-C catalyst showed the highest Au mass-based catalytic activity. The following trend was found at 448 K: Au/N-C > Au/SiO2 > Au/Al2O3, Au/C. The trend for the selectivity in hydrogen production was different: Au/C (99.5%) > Au/Al2O3 (98.0%) > Au/N-C (96.3%) > Au/SiO2 (83.0%). According to XPS data the Au was present in metallic state in all catalysts after the reaction. TEM analysis revealed that the use of the N-C support allowed obtaining highly dispersed Au nanoparticles with a mean size of about 2 nm, which was close to those for the Au catalysts on the oxide supports. However, it was by a factor of 5 smaller than that for the Au/C catalyst. The difference in dispersion could explain the difference in the catalytic activity for the carbon-based catalysts. Additionally, the high activity of the Au/N-C catalyst could be related to the presence of pyridinic type nitrogen on the N-doped carbon surface, which activates the formic acid molecule forming pyridinium formate species further interacting with Au. This was confirmed by density functional theory (DFT) calculations. The results of this study may assist the development of novel Au catalysts for different catalytic reactions. Full article
(This article belongs to the Special Issue Metal Catalysts for Renewable Energies)
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Open AccessFeature PaperArticle
Structure-Sensitivity of CO2 Methanation over Nanostructured Ni Supported on CeO2 Nanorods
Catalysts 2019, 9(4), 375; https://doi.org/10.3390/catal9040375
Received: 28 March 2019 / Revised: 17 April 2019 / Accepted: 18 April 2019 / Published: 22 April 2019
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Abstract
Ni-based oxides are widely investigated as catalysts for CO2 methanation due to their high activity, high selectivity and low cost. The catalytic performances of Ni-based catalysts depend on support properties that strongly influence the dispersion of the catalytic active phase and the [...] Read more.
Ni-based oxides are widely investigated as catalysts for CO2 methanation due to their high activity, high selectivity and low cost. The catalytic performances of Ni-based catalysts depend on support properties that strongly influence the dispersion of the catalytic active phase and the Ni–support interaction. Although the CO2 methanation is widely studied, the structure sensitivity of methanation on nickel is not completely assessed. Ni/CeO2 nanorods with different nickel/ceria molar ratios (0.05, 0.10, 0.20, 0.30) were prepared by one-pot hydrothermal synthesis. The effect of nickel content and metal particle size on catalytic activity and selectivity for CO2 methanation were studied using CO2:H2 = 1:4 stoichiometric ratio at high space velocity (300 L g−1 h−1). Sample structure and morphology were studied by X-ray diffraction (XRD), Brunauer–Emmet–Teller (BET) analysis, field-emission scanning electron microscopy/energy-dispersive spectroscopy (FE-SEM/EDS), H2-temperature programmed reduction (TPR), H2-temperature-programmed desorption (TPD). Both the CO production and the turnover frequency appear depending on nickel particle size, suggesting a structure sensitivity of the CO2 methanation on nickel supported on ceria. Full article
(This article belongs to the Special Issue Supported Catalysts for Carbon Oxides Methanation)
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Open AccessArticle
Liquid-Phase Catalytic Oxidation of Limonene to Carvone over ZIF-67(Co)
Catalysts 2019, 9(4), 374; https://doi.org/10.3390/catal9040374
Received: 15 March 2019 / Revised: 6 April 2019 / Accepted: 16 April 2019 / Published: 21 April 2019
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Abstract
Liquid-phase catalytic oxidation of limonene was carried out under mild conditions, and carvone was produced in the presence of ZIF-67(Co), cobalt based zeolitic imidazolate framework, as catalyst, using t-butyl hydroperoxide (t-BHP) as oxidant and benzene as solvent. As a heterogeneous catalyst, the zeolitic [...] Read more.
Liquid-phase catalytic oxidation of limonene was carried out under mild conditions, and carvone was produced in the presence of ZIF-67(Co), cobalt based zeolitic imidazolate framework, as catalyst, using t-butyl hydroperoxide (t-BHP) as oxidant and benzene as solvent. As a heterogeneous catalyst, the zeolitic imidazolate framework ZIF-67(Co) exhibited reasonable substrate–product selectivity (55.4%) and conversion (29.8%). Finally, the X-ray diffraction patterns of the catalyst before and after proved that ZIF-67(Co) acted as a heterogeneous catalyst, and can be reused without losing its activity to a great extent. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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Open AccessArticle
Acid–Base Catalytic Effects on Reduction of Methanol in Hot Water
Catalysts 2019, 9(4), 373; https://doi.org/10.3390/catal9040373
Received: 9 April 2019 / Revised: 16 April 2019 / Accepted: 17 April 2019 / Published: 21 April 2019
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Abstract
We have performed a number of quantum chemical simulations to examine the reduction process of methanol in hot water. Methanol is converted into a methane by capturing a hydrogen molecule and leaving a water molecule behind. The required energy for the reduction is [...] Read more.
We have performed a number of quantum chemical simulations to examine the reduction process of methanol in hot water. Methanol is converted into a methane by capturing a hydrogen molecule and leaving a water molecule behind. The required energy for the reduction is too high to proceed in the gas phase. The energy barrier for the reduction of methanol is reduced by the catalytic effect of water molecules when we consider the reduction in aqueous solution. However, the calculated reduction rate is still much slower than that found experimentally. The ion product of water tends to increase in hot water, even though it eventually decreases at the high temperature of supercritical water. It is valuable to consider the acid–base catalytic effects on the reduction of methanol in hot water. The significant reduction of the energy barrier is accomplished by the acid–base catalytic effects due to hydronium or hydroxyde. Mean collision time between a hydronium and a methanol in hot water is shorter than the reduction time, during which a methanol is converted into a methane. The calculated reduction rate with the acid–base catalytic effects agrees well with that determined by laboratory experiments. The present study reveals a crucial role of the acid–base catalytic effects on reactions in hot water. Full article
(This article belongs to the Section Computational Catalysis)
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Open AccessArticle
Fly Ash-Based Geopolymers as Sustainable Bifunctional Heterogeneous Catalysts and Their Reactivity in Friedel-Crafts Acylation Reactions
Catalysts 2019, 9(4), 372; https://doi.org/10.3390/catal9040372
Received: 20 March 2019 / Revised: 10 April 2019 / Accepted: 17 April 2019 / Published: 19 April 2019
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Abstract
This study presents the synthesis, characteristics and catalytic reactivity of sustainable bifunctional heterogeneous catalysts derived from coal fly ash-based geopolymer, particularly those with a high Ca content (C-class) fly ash. The developed catalysts were synthesized at room temperature and pressure in a simple [...] Read more.
This study presents the synthesis, characteristics and catalytic reactivity of sustainable bifunctional heterogeneous catalysts derived from coal fly ash-based geopolymer, particularly those with a high Ca content (C-class) fly ash. The developed catalysts were synthesized at room temperature and pressure in a simple ecologically-benign procedure and their reactivity was evaluated in the Friedel-Crafts acylation of various arenes. These catalysts can be produced with multilevel porous architecture, and a combination of acidic and redox active sites allowing their use as bifunctional catalysts. The acidic sites (Lewis and Brønsted acidic sites) were generated within the catalyst framework by ion-exchange followed by thermal treatment, and redox sites that originated from the catalytically reactive fly ash components. The developed catalysts demonstrated higher reactivity than other commonly used solid catalysts such as Metal-zeolite and Metal-mesoporous silicate, heteropolyacids and zeolite imidazole frameworks (ZIF). Full article
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Open AccessArticle
Facet-Dependent Reactivity of Fe2O3/CeO2 Nanocomposites: Effect of Ceria Morphology on CO Oxidation
Catalysts 2019, 9(4), 371; https://doi.org/10.3390/catal9040371
Received: 19 March 2019 / Revised: 11 April 2019 / Accepted: 15 April 2019 / Published: 19 April 2019
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Abstract
Ceria has been widely studied either as catalyst itself or support of various active phases in many catalytic reactions, due to its unique redox and surface properties in conjunction to its lower cost, compared to noble metal-based catalytic systems. The rational design of [...] Read more.
Ceria has been widely studied either as catalyst itself or support of various active phases in many catalytic reactions, due to its unique redox and surface properties in conjunction to its lower cost, compared to noble metal-based catalytic systems. The rational design of catalytic materials, through appropriate tailoring of the particles’ shape and size, in order to acquire highly efficient nanocatalysts, is of major significance. Iron is considered to be one of the cheapest transition metals while its interaction with ceria support and their shape-dependent catalytic activity has not been fully investigated. In this work, we report on ceria nanostructures morphological effects (cubes, polyhedra, rods) on the textural, structural, surface, redox properties and, consequently, on the CO oxidation performance of the iron-ceria mixed oxides (Fe2O3/CeO2). A full characterization study involving N2 adsorption at –196 °C, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), temperature programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) was performed. The results clearly revealed the key role of support morphology on the physicochemical properties and the catalytic behavior of the iron-ceria binary system, with the rod-shaped sample exhibiting the highest catalytic performance, both in terms of conversion and specific activity, due to its improved reducibility and oxygen mobility, along with its abundance in Fe2+ species. Full article
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Open AccessReview
Hierarchical Nanostructured Photocatalysts for CO2 Photoreduction
Catalysts 2019, 9(4), 370; https://doi.org/10.3390/catal9040370
Received: 31 March 2019 / Revised: 17 April 2019 / Accepted: 17 April 2019 / Published: 19 April 2019
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Abstract
Practical implementation of CO2 photoreduction technologies requires low-cost, highly efficient, and robust photocatalysts. High surface area photocatalysts are notable in that they offer abundant active sites and enhanced light harvesting. Here we summarize the progress in CO2 photoreduction with respect to [...] Read more.
Practical implementation of CO2 photoreduction technologies requires low-cost, highly efficient, and robust photocatalysts. High surface area photocatalysts are notable in that they offer abundant active sites and enhanced light harvesting. Here we summarize the progress in CO2 photoreduction with respect to synthesis and application of hierarchical nanostructured photocatalysts. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Energy Conversion)
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Open AccessArticle
Modeling and Order Reduction for the Thermodynamics of a Diesel Oxidation Catalyst with Hydrocarbon Dosing
Catalysts 2019, 9(4), 369; https://doi.org/10.3390/catal9040369
Received: 21 February 2019 / Revised: 8 April 2019 / Accepted: 13 April 2019 / Published: 18 April 2019
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Abstract
This paper presents an order reduction for the thermal dynamics of a diesel oxidation catalyst (DOC) with hydrocarbon (HC) dosing. The original model includes the pyrolysis of diesel droplets and a wall storage process in the upstream of the DOC. The order reduction [...] Read more.
This paper presents an order reduction for the thermal dynamics of a diesel oxidation catalyst (DOC) with hydrocarbon (HC) dosing. The original model includes the pyrolysis of diesel droplets and a wall storage process in the upstream of the DOC. The order reduction process is derived from the thermodynamics model of the DOC for further control design. The results are compared with experimental data. It is found that the DOC can be simplified as a second-order model using the HC dosing model, which has more than 94% fitness, reflecting the thermodynamics of the system. According to this research, the DOC thermal dynamics can be considered to be equivalent to a time-varying second-order system for the investigation. The second-order parameters of K, Tw, and ζ are also investigated in this paper. Full article
(This article belongs to the Special Issue Reactors and Models in Catalysis)
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Open AccessArticle
Laccase-Catalyzed Oxidation of Mixed Aqueous Phenolic Substrates at Low Concentrations
Catalysts 2019, 9(4), 368; https://doi.org/10.3390/catal9040368
Received: 13 March 2019 / Revised: 8 April 2019 / Accepted: 15 April 2019 / Published: 18 April 2019
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Abstract
It has been proposed that Trametes versicolor laccase can be used to detoxify wastewaters that are contaminated with phenolic pollutants. However, the oxidation of phenols at low concentrations may be impacted if other substrates tend to interfere with or enhance the oxidation of [...] Read more.
It has been proposed that Trametes versicolor laccase can be used to detoxify wastewaters that are contaminated with phenolic pollutants. However, the oxidation of phenols at low concentrations may be impacted if other substrates tend to interfere with or enhance the oxidation of the target substrate. To test this, experiments were conducted to evaluate effects arising from the simultaneous presence of mixed substrates including phenol (P), estradiol (E2), cumylphenol (CP), and triclosan (TCL), each of which are characterized by different rates of oxidation and tendencies to inactivate laccase. Slower and faster substrates were found to have only minor negative impacts upon the rate of conversion of targeted substrates, except where they tended to cause inactivation. No enhancements in substrate oxidation were observed. A multi-substrate kinetic model was shown to be able to accurately predict the time course of reactions of mixed substrates over extended periods at micromolar and sub-micromolar concentrations, except when estradiol and triclosan were simultaneously present. In this case, more enzyme inactivation was observed than would be expected from the oxidation of individual substrates alone. The utility of the model for providing insights into the reaction phenomenon and for evaluating the feasibility of oxidizing targeted substrates in the presence of other substrates is demonstrated. Full article
(This article belongs to the Special Issue Reactors and Models in Catalysis)
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Open AccessArticle
Preparation of Metal Amalgam Electrodes and Their Selective Electrocatalytic CO2 Reduction for Formate Production
Catalysts 2019, 9(4), 367; https://doi.org/10.3390/catal9040367
Received: 28 March 2019 / Revised: 15 April 2019 / Accepted: 16 April 2019 / Published: 18 April 2019
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Abstract
Electrochemical CO2 reduction to produce formate ions has studied for the sustainable carbon cycle. Mercury in the liquid state is known to be an active metallic component to selectively convert CO2 to formate ions, but it is not scalable to use [...] Read more.
Electrochemical CO2 reduction to produce formate ions has studied for the sustainable carbon cycle. Mercury in the liquid state is known to be an active metallic component to selectively convert CO2 to formate ions, but it is not scalable to use as an electrode in electrochemical CO2 reduction. Therefore, scalable amalgam electrodes with different base metals are tested to produce formate by an electrochemical CO2 reduction. The amalgam electrodes are prepared by the electrodeposition of Hg on the pre-electrodeposited Pd, Au, Pt and Cu nanoparticles on the glassy carbon. The formate faradaic efficiency with the Pd, Au, Pt and Cu is lower than 25%, while the one with the respective metal amalgams is higher than 50%. Pd amalgam among the tested samples shows the highest formate faradic efficiency and current density. The formate faradaic efficiency is recorded 85% at −2.1 V vs SCE and the formate current density is −6.9 mA cm−2. It is concluded that Pd2Hg5 alloy on the Pd amalgam electrode is an active phase for formate production in the electrochemical CO2 reduction. Full article
(This article belongs to the Special Issue Catalysis and Catalytic Processes for CO2 Conversion)
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Open AccessArticle
Tuning Selectivity of Maleic Anhydride Hydrogenation Reaction over Ni/Sc-Doped ZrO2 Catalysts
Catalysts 2019, 9(4), 366; https://doi.org/10.3390/catal9040366
Received: 17 March 2019 / Revised: 10 April 2019 / Accepted: 16 April 2019 / Published: 18 April 2019
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Abstract
A series of Sc-doped ZrO2 supports, with Sc2O3 content in the range of 0 to 7.5% (mol/mol), were prepared using the hydrothermal method. Ni/Sc-doped ZrO2 catalysts with nickel loading of 10% (w/w) were prepared [...] Read more.
A series of Sc-doped ZrO2 supports, with Sc2O3 content in the range of 0 to 7.5% (mol/mol), were prepared using the hydrothermal method. Ni/Sc-doped ZrO2 catalysts with nickel loading of 10% (w/w) were prepared using impregnation method, and characterized with the use of XRD, Raman, H2 temperature-programmed reduction (H2-TPR), H2 temperature-programmed desorption (H2-TPD), XPS, and in situ FT-IR techniques. The catalytic performances of Ni/Sc-doped ZrO2 catalysts in maleic anhydride hydrogenation were tested. The results showed that the introduction of Sc3+ into ZrO2 support could effectively manipulate the distribution of maleic anhydride hydrogenation products. γ-butyrolactone was the major hydrogenation product over Sc-free Ni/ZrO2 catalyst with selectivity as high as 65.8% at 210 °C and 5 MPa of H2 pressure. The Ni/Sc-doped ZrO2 catalyst, with 7.5 mol% of Sc2O3 content, selectively catalyzed maleic anhydride hydrogenation to succinic anhydride, the selectivity towards succinic anhydride was up to 97.6% under the same reaction condition. The results of the catalysts’ structure–activity relationships revealed that there was an interdependence between the surface structure of ZrO2-based support and the C=O hydrogenation performance of the ZrO2-based supported nickel catalysts. By controlling the Sc2O3 content, the surface structure of ZrO2-based support could be regulated effectively. The different surface structure of ZrO2-based supports, resulted in the different degree of interaction between the nickel species and ZrO2-based supports; furthermore, the different interaction led to the different surface oxygen vacancies electron properties of ZrO2-based supported nickel catalysts and the C=O hydrogenation activity of the catalyst. This result provides new insight into the effect of ZrO2 support on the selective hydrogenation activity of ZrO2-supported metal catalysts and contributes to the design of selective hydrogenation catalysts for other unsaturated carbonyl compounds. Full article
(This article belongs to the Special Issue Catalysis and Fine Chemicals)
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Open AccessArticle
BaTi0.8B0.2O3 (B = Mn, Fe, Co, Cu) LNT Catalysts: Effect of Partial Ti Substitution on NOx Storage Capacity
Catalysts 2019, 9(4), 365; https://doi.org/10.3390/catal9040365
Received: 6 March 2019 / Revised: 5 April 2019 / Accepted: 16 April 2019 / Published: 18 April 2019
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Abstract
The effect of partial Ti substitution by Mn, Fe, Co, or Cu on the NOx storage capacity (NSC) of a BaTi0.8B0.2O3 lean NOx trap (LNT) catalyst has been analyzed. The BaTi0.8B0.2O3 catalysts were [...] Read more.
The effect of partial Ti substitution by Mn, Fe, Co, or Cu on the NOx storage capacity (NSC) of a BaTi0.8B0.2O3 lean NOx trap (LNT) catalyst has been analyzed. The BaTi0.8B0.2O3 catalysts were prepared using the Pechini’s sol–gel method for aqueous media. The characterization of the catalysts (BET, ICP-OES, XRD and XPS) reveals that: i) the partial substitution of Ti by Mn, Co, or Fe changes the perovskite structure from tetragonal to cubic, whilst Cu distorts the raw tetragonal structure and promotes the segregation of Ba2TiO4 (which is an active phase for NOx storage) as a minority phase and ii) the amount of oxygen vacancies increases after partial Ti substitution, with the BaTi0.8Cu0.2O3 catalyst featuring the largest amount. The BaTi0.8Cu0.2O3 catalyst shows the highest NSC at 400 °C, based on NOx storage cyclic tests, which is within the range of highly active noble metal-based catalysts. Full article
(This article belongs to the Special Issue Catalysis by Metals on Perovskite-Type Oxides)
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Open AccessArticle
H-ZSM-5 Materials Embedded in an Amorphous Silica Matrix: Highly Selective Catalysts for Propylene in Methanol-to-Olefin Process
Catalysts 2019, 9(4), 364; https://doi.org/10.3390/catal9040364
Received: 15 March 2019 / Revised: 12 April 2019 / Accepted: 13 April 2019 / Published: 17 April 2019
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Abstract
H-ZSM-5 materials embedded in an amorphous silica were successfully synthesized with three different Si/Al ratios (i.e., 40, 45, and 50). The presence of the MFI structure in the synthesized samples was confirmed by X-ray diffraction (XRD), Fourier transform infra-red (FT-IR), and solid state-nuclear [...] Read more.
H-ZSM-5 materials embedded in an amorphous silica were successfully synthesized with three different Si/Al ratios (i.e., 40, 45, and 50). The presence of the MFI structure in the synthesized samples was confirmed by X-ray diffraction (XRD), Fourier transform infra-red (FT-IR), and solid state-nuclear magnetic resonance (SSNMR) techniques. The morphology and textural properties of the samples were investigated by scanning electron microscopy (SEM), TEM, and N2-physisorption measurements. Furthermore, acidic properties of the synthesized catalysts have been studied by NH3-TPD and FT-IR spectroscopy of CO adsorption studies. Variation of the Si/Al ratio affected the crystal morphology, porosity, and particle size, as well as the strength and distribution of acid sites. The synthesized zeolite materials possessed low acid-site density and exhibited high catalytic activity in the methanol-to-olefin (MTO) reaction. To study the intermediate species responsible for catalyst deactivation, the MTO reaction was carried out at high temperature (500 °C) to accelerate catalyst deactivation. Interestingly, the synthesized catalysts offered high selectivity towards the formation of propylene (C3=), in comparison to a commercial microporous crystalline H-ZSM-5 with Si/Al = 40, under the same reaction conditions. The synthesized H-ZSM-5 materials offered a selectivity ratio of C3=/C2= 12, while it is around 2 for the commercial H-ZSM-5 sample. The formation of hydrocarbon species during MTO reaction over zeolite samples has been systematically studied with operando UV-vis spectroscopy and online gas chromatography. It is proposed that the strength and type of acid sites of catalyst play a role in propylene selectivity as well as the fast growing of active intermediate species. The effective conversion of methanol into propylene in the case of synthesized H-ZSM-5 materials was observed due to possession of weak acid sites. This effect is more pronounced in H-ZSM-5 sample with a Si/Al ratio of 45. Full article
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Open AccessFeature PaperArticle
Oxidative Coupling of Methane over Mn2O3-Na2WO4/SiC Catalysts
Catalysts 2019, 9(4), 363; https://doi.org/10.3390/catal9040363
Received: 27 March 2019 / Revised: 10 April 2019 / Accepted: 11 April 2019 / Published: 15 April 2019
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Abstract
The oxidative coupling of methane (OCM) is operated at high temperatures and is a highly exothermic reaction; thus, hotspots form on the catalyst surface during reaction unless the produced heat is removed. It is crucial to control the heat formed because surface hotspots [...] Read more.
The oxidative coupling of methane (OCM) is operated at high temperatures and is a highly exothermic reaction; thus, hotspots form on the catalyst surface during reaction unless the produced heat is removed. It is crucial to control the heat formed because surface hotspots can degrade catalytic performance. Herein, we report the preparation of Mn2O3-Na2WO4/SiC catalysts using SiC, which has high thermal conductivity and good stability at high temperatures, and the catalyst was applied to the OCM. Two Mn2O3-Na2WO4/SiC catalysts were prepared by wet-impregnation on SiC supports having different particle sizes. For comparison, the Mn2O3-Na2WO4/SiO2 catalyst was also prepared by the same method. The catalysts were analyzed by nitrogen adsorption–desorption, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The transformation of SiC into α-cristobalite was observed for the Mn2O3-Na2WO4/SiC catalysts. Because SiC was completely converted into α-cristobalite for the nano-sized SiC-supported Mn2O3-Na2WO4 catalyst, the catalytic performance for the OCM reaction of Mn2O3-Na2WO4/n-SiC was similar to that of Mn2O3-Na2WO4/SiO2. However, only the surface layer of SiC was transformed into α-cristobalite for the micro-sized SiC (m-SiC) in Mn2O3-Na2WO4/m-SiC, resulting in a [email protected]α-cristobalite core–shell structure. The Mn2O3-Na2WO4/m-SiC showed higher methane conversion and C2+ yield at 800 and 850 °C than Mn2O3-Na2WO4/SiO2. Full article
(This article belongs to the Special Issue Catalysts for Stable Molecules (CO2, CO, CH4, NH3) Conversion)
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Open AccessArticle
Oxychlorination Redispersion of Pt Catalysts: Surface Species and Pt-Support Interactions Characterized by X-ray Absorption and FT-IR Spectroscopy
Catalysts 2019, 9(4), 362; https://doi.org/10.3390/catal9040362
Received: 15 March 2019 / Revised: 10 April 2019 / Accepted: 11 April 2019 / Published: 15 April 2019
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Abstract
To help elucidate the oxychlorination redispersion reaction mechanism, the surface species formed on the surface of γ-Al2O3 was characterized by X-ray absorption spectroscopy (XAS). The efficacy of redispersion was assessed by the Pt–Pt coordination number (CNPt–Pt) of redispersed, [...] Read more.
To help elucidate the oxychlorination redispersion reaction mechanism, the surface species formed on the surface of γ-Al2O3 was characterized by X-ray absorption spectroscopy (XAS). The efficacy of redispersion was assessed by the Pt–Pt coordination number (CNPt–Pt) of redispersed, and then reduced samples. A nearly fully redispersed complex (Ptrd52) was prepared by treating a sintered model Pt/γ-Al2O3 catalyst at 520 °C, Air/EDC (ethylene dichloride) of 30, and WHSV (Weight Hourly Space Velocity) of 0.07 h−1 for 16 h. For investigating temperature effects, samples treated at 460 (Ptrd46) and 560 °C (Ptrd56) were also prepared for comparison. It was found that, while an octahedral resembling Pt(Os)3–4(O–Cl)2–3 (Os represents support oxygen or hydroxyl oxygen) complex was formed on γ-Al2O3 of Ptrd52, less O–Cl ligands were formed on the redispersed complexes, Ptrd46 and Ptrd56. A negative correlation of CNPt–Pt with CNPt–Cl* (Cl* represents the Cl atom in O–Cl ligand) for these three samples further suggested that the formation of Pt–O–Cl played a key role in the redispersion process. Pt–O–Cl could be formed in the reaction of reactive Cl⋅ and PtO2. At an operation temperature of lower-than-optimal temperatures of 520 °C, less Cl2 dissociation and less O–Cl ligands were formed. On the other hand, higher temperatures may facilitate Cl2 dissociation, but reduce the equilibrium conversion of HCl to Cl2, leading to increased HCl reaction with Pt (PtO2) clusters to form Pt–Cl (Cl is the atom bonded directly to Pt), and decreased formation of Pt–O–Cl. Full article
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