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Catalysts, Volume 9, Issue 11 (November 2019) – 97 articles

Cover Story (view full-size image): We report an in situ electron paramagnetic resonance (EPR) study of a low-cost, high-stability cobalt oxide electrodeposited material (Co-Pi) that oxidizes water at neutral pH and low over-potential, representing a promising system for future large-scale water splitting applications. A custom-made in situ spectroelectrochemical EPR cell was employed to monitor oxidation state and structural changes in electrodeposited catalyst films vs. an externally applied potential bias. The extent of Co(II) to Co(IV) conversion at potentials commensurate with electrocatalytic O2 evolution was consistent with the role of Co(IV) as an intermediate in the water oxidation reaction. View this paper.
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Article
Investigation of Thermal Stability and Reactivity of Rh Nanoclusters on an Ultrathin Alumina Film
Catalysts 2019, 9(11), 971; https://doi.org/10.3390/catal9110971 - 18 Nov 2019
Cited by 2 | Viewed by 826
Abstract
We studied the structural and morphological evolution of Rh clusters on an ordered ultrathin alumina film grown on NiAl(100) in annealing processes, under ultrahigh vacuum conditions and with various surface probe techniques. The Rh clusters, prepared on vapor deposition of Rh onto the [...] Read more.
We studied the structural and morphological evolution of Rh clusters on an ordered ultrathin alumina film grown on NiAl(100) in annealing processes, under ultrahigh vacuum conditions and with various surface probe techniques. The Rh clusters, prepared on vapor deposition of Rh onto the alumina film at 300 K, had an fcc phase and grew in the (100) orientation; the annealing altered the cluster structure little—the lattice parameter decreased by a factor <2%—but the cluster morphology significantly. With elevated temperature, small clusters (diameter ≤1.5 nm) decreased little in size; in contrast, large clusters (diameter ≥2.0 nm) varied in a complex manner—their mean diameter decreased to about 1.5 nm on annealing to 450 K, despite their similar height, while it increased to above 2.0 nm at temperature ≥570 K. This atypical decrease in size was governed predominantly by energetics. Such a reduced size enhanced the total surface area as well as the reactivity of the clusters toward methanol decomposition, so increased the production of D2 (H2) and CO from decomposed methanol-d4 (or methanol). The result implies a higher temperature tolerance for Rh clusters on the alumina film and a practical approach to prepare small Rh clusters with high reactivity. Full article
(This article belongs to the Special Issue Recent Developments in Rh Catalysts)
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Article
Low-Level Organic Solvents Improve Multienzyme Whole-Cell Catalytic Synthesis of Myricetin-7-O-Glucuronide
Catalysts 2019, 9(11), 970; https://doi.org/10.3390/catal9110970 - 18 Nov 2019
Cited by 4 | Viewed by 953
Abstract
Multienzyme whole-cell biocatalysts are preferred in industrial applications, and two major concerns regarding the use of these biocatalysts, cell viability and cell membrane integrity, must be addressed. In this work, the transformation of myricetin to myricetin-7-O-glucuronide catalyzed by an engineered Escherichia [...] Read more.
Multienzyme whole-cell biocatalysts are preferred in industrial applications, and two major concerns regarding the use of these biocatalysts, cell viability and cell membrane integrity, must be addressed. In this work, the transformation of myricetin to myricetin-7-O-glucuronide catalyzed by an engineered Escherichia coli strain was taken as the model reaction to examine the impacts of low-level organic solvents on whole-cell biocatalysis. Low-level organic solvents (2%, v/v) showed a significant increase (roughly 13-fold) in myricetin-7-O-glucuronide yields. No obvious compromises of cellular viability and integrity were observed by a flow cytometry assay or in the determination of extracellular protein leakage, suggesting the addition of low-level organic solvents accommodates whole E. coli cells. Furthermore, a scaled-up reaction was conducted to test the capability and efficiency of whole-cell catalysis in the presence of organic solvents. This study presents a promising and simple means to enhance the productivity of multienzyme whole-cell catalysis without losing the barrier functions of the cell membrane. Full article
(This article belongs to the Special Issue Novel Enzyme and Whole-Cell Biocatalysts)
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Article
Enhancement of GAD Storage Stability with Immobilization on PDA-Coated Superparamagnetic Magnetite Nanoparticles
Catalysts 2019, 9(11), 969; https://doi.org/10.3390/catal9110969 - 18 Nov 2019
Cited by 2 | Viewed by 965
Abstract
To improve the storage stability of glutamic acid decarboxylase (GAD), superparamagnetic magnetite (Fe3O4) nanoparticles were synthesized by co-precipitation method and coated with polydopamine (PDA) for GAD immobilization. Dynamic light scattering and transmission electron microscopy were used to determine size [...] Read more.
To improve the storage stability of glutamic acid decarboxylase (GAD), superparamagnetic magnetite (Fe3O4) nanoparticles were synthesized by co-precipitation method and coated with polydopamine (PDA) for GAD immobilization. Dynamic light scattering and transmission electron microscopy were used to determine size of the nanoparticles, which were approximately 10 nm, increasing to 15 nm after PDA-coating and to 20 nm upon GAD binding. Vibrational scanning measurements significantly represented the superparamagnetic behavior of the Fe3O4, and X-ray diffraction analysis confirmed that the crystalline structure before and after coating with PDA and the further immobilization of GAD remained the same. Thermogravimetric analysis and Fourier-transform infrared spectroscopy proved that the PDA-coating on Fe3O4 and further immobilization of GAD were successful. After immobilization, the enzyme can be used with a relative specific activity of 40.7% after five successive uses. The immobilized enzyme retained relative specific activity of about 50.5% after 15 days of storage at 4 °C, while free enzyme showed no relative specific activity after two days of storage. The GAD immobilization on PDA-coated magnetite nanoparticles was reported for the improvement of enzyme storage stability for the first time. Full article
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Article
Ca-Doped CrOX/γ-Al2O3 Catalysts with Improved Dehydrogenation Performance for the Conversion of Isobutane to Isobutene
Catalysts 2019, 9(11), 968; https://doi.org/10.3390/catal9110968 - 16 Nov 2019
Viewed by 1001
Abstract
The dehydrogenation of low-carbon alkane to obtain olefins is an effective way to meet the steadily increasing demand of these building blocks in chemical industry. In this study, Ca-doped CrOx/γ-Al2O3 catalysts were fabricated via a one-pot method by [...] Read more.
The dehydrogenation of low-carbon alkane to obtain olefins is an effective way to meet the steadily increasing demand of these building blocks in chemical industry. In this study, Ca-doped CrOx/γ-Al2O3 catalysts were fabricated via a one-pot method by employing Cr(OH)3 as the precursor, and their catalytic performances were tested in the dehydrogenation of isobutane to isobutene (DITI) process. The prepared catalysts were intensively characterized by XRD, SEM, NH3-TPD, H2-TPR, low-temperature N2 adsorption–desorption, etc. These characterization results indicated that the doping of Ca into the CrOx/γ-Al2O3 catalysts could tune the acidity properties of the prepared catalysts and enhance the interaction between the active species and support. The Ca-doped CrOx/γ-Al2O3 catalysts, especially the Ca2-Cr/γ-Al2O3 catalyst with a Ca doping of 2 wt%, exhibited a superior catalytic performance in the DITI process in comparison with the undoped catalyst. Full article
(This article belongs to the Special Issue Metal/Metal Oxide-Support Interactions in Heterogeneous Catalysis)
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Article
Second-Generation Manganese(III) Porphyrins Bearing 3,5-Dichloropyridyl Units: Innovative Homogeneous and Heterogeneous Catalysts for the Epoxidation of Alkenes
Catalysts 2019, 9(11), 967; https://doi.org/10.3390/catal9110967 - 16 Nov 2019
Cited by 3 | Viewed by 950
Abstract
The synthesis, characterisation and homogeneous catalytic oxidation results of two manganese(III) porphyrins of the so-called second-generation of metalloporphyrin catalysts, containing one or four 3,5-dichloropyridyl substituents at the meso positions are reported for the first time. The catalytic efficiency of these novel manganese(III) porphyrins [...] Read more.
The synthesis, characterisation and homogeneous catalytic oxidation results of two manganese(III) porphyrins of the so-called second-generation of metalloporphyrin catalysts, containing one or four 3,5-dichloropyridyl substituents at the meso positions are reported for the first time. The catalytic efficiency of these novel manganese(III) porphyrins was evaluated in the oxidation of cyclooctene and styrene using aqueous hydrogen peroxide as the oxidant, under homogeneous conditions. High conversions were obtained in the presence of both catalysts, obtaining the corresponding epoxide as the major product. The asymmetric metalloporphyrin, chloro[5,10,15-tris(2,6-dichlorophenyl)-20-(3,5-dichloropyridin-4-yl)porphyrinate]manganese(III), CAT-4, evidences a similar activity to that obtained with the well-known and highly efficient second-generation metalloporphyrin catalyst, chloro[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinate]manganese(III), CAT-2. CAT-4 was covalently attached onto Merrifield resin and 3-bromopropylsilica supports. The solid materials obtained were characterized by several techniques including diffuse reflectance, UV—VIS spectrophotometry, SEM and XPS. The catalytic results for the oxidation of cyclooctene and styrene using the immobilized catalysts are also presented. The Merrifield-supported catalyst showed to be very efficient, leading to five catalytic cycles in the oxidation of cyclooctene, using tert-butyl hydroperoxide as the oxidant. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
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Communication
Enhanced Performance of Immobilized Xylanase/Filter Paper-ase on a Magnetic Chitosan Support
Catalysts 2019, 9(11), 966; https://doi.org/10.3390/catal9110966 - 16 Nov 2019
Cited by 2 | Viewed by 884
Abstract
Enzyme immobilization on different supports has emerged as an efficient and cost-effective tool to improve their stability and reuse capacity. This work aimed to produce a stable immobilized multienzymatic system of xylanase and filter paper-ase (FPase) onto magnetic chitosan using genipin as a [...] Read more.
Enzyme immobilization on different supports has emerged as an efficient and cost-effective tool to improve their stability and reuse capacity. This work aimed to produce a stable immobilized multienzymatic system of xylanase and filter paper-ase (FPase) onto magnetic chitosan using genipin as a cross-linking agent and to evaluate its biochemical properties and reuse capacity. A mixture of chitosan magnetic nanoparticles, xylanase, and FPase was covalently bonded using genipin. Immobilization yield and efficiency were quantified. The activity of free and immobilized enzymes was quantified at different values of pH, temperature, substrate concentration (Km and Vmax), and reuse cycles. The immobilization yield, immobilization efficiency, and activity recovery were 145.3% ± 3.06%, 14.8% ± 0.81%, and 21.5% ± 0.72%, respectively, measured as the total hydrolytic activity. Immobilization confers resistance to acidic/basic conditions and thermal stability compared to the free form. Immobilization improved 3.5-fold and 78-fold the catalytic efficiency (Kcat/Km) of the xylanase and filter paper-ase activities, while immobilized xylanase and FPase could be reused for 34 min and 43 min, respectively. Cross-linking significantly improved the biochemical properties of immobilized enzymes, combined with their simplicity of reuse due to the paramagnetic property of the support. Multienzyme immobilization technology is an important issue for industrial applications. Full article
(This article belongs to the Special Issue Immobilization of Enzymes)
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Article
Assessment of Degradation Behavior for Acetylsalicylic Acid Using a Plasma in Liquid Process
Catalysts 2019, 9(11), 965; https://doi.org/10.3390/catal9110965 - 16 Nov 2019
Cited by 2 | Viewed by 971
Abstract
Acetylsalicylic acid (ASA) is a pharmacologically active compound. In this study, ASA was decomposed effectively using a plasma in liquid phase process with hydrogen peroxide and TiO2 photocatalyst. Increasing the electrical power conditions (frequency, applied voltage, and pulse width) promoted plasma generation, [...] Read more.
Acetylsalicylic acid (ASA) is a pharmacologically active compound. In this study, ASA was decomposed effectively using a plasma in liquid phase process with hydrogen peroxide and TiO2 photocatalyst. Increasing the electrical power conditions (frequency, applied voltage, and pulse width) promoted plasma generation, which increased the rate of ASA decomposition. The added hydrogen peroxide increased the rate of ASA degradation, but injecting an excess decreased the degradation rate due to a scavenger effect. Although there was an initial increase in the decomposition efficiency by the addition of TiO2 powder, the addition of an excessive amount inhibited the generation of plasma and decreased the degradation rate. The simultaneous addition of H2O2 and TiO2 powder resulted in the highest degradation efficiency. We suggest that ASA is converted to salicylic acid through demethylation by hydroxyl radicals and is finally mineralized to carbon dioxide and water via 2,4-dihydroxy benzoic acid and low molecular acids. Full article
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Article
Photocatalytic Removal of Methyl Orange Azo Dye with Simultaneous Hydrogen Production Using Ru-Modified ZnO Photocatalyst
Catalysts 2019, 9(11), 964; https://doi.org/10.3390/catal9110964 - 15 Nov 2019
Cited by 8 | Viewed by 925
Abstract
The aim of this work is to demonstrate the effectiveness of the photocatalytic process in the Methyl Orange azo dye degradation and simultaneous H2 production by using ZnO doped with ruthenium. Ru-modified ZnO photocatalysts were prepared by precipitation method and were characterized [...] Read more.
The aim of this work is to demonstrate the effectiveness of the photocatalytic process in the Methyl Orange azo dye degradation and simultaneous H2 production by using ZnO doped with ruthenium. Ru-modified ZnO photocatalysts were prepared by precipitation method and were characterized by different techniques (XRF, Raman, XRD, N2 adsorption at −196 °C, and UV–vis DRS). The experiments were carried out in a pyrex cylindrical reactor equipped with a nitrogen distributor device and irradiated by four UV lamps with the main wavelength emission at 365 nm. Different Ru amounts (from 0.10 to 0.50 mol%) were tested in order to establish the optimal amount of the metal to be used for the ZnO doping. The photocatalytic activity was evaluated both in terms of Methyl Orange removal and hydrogen production. The experimental results showed that the best activity, both in terms of H2 production and Methyl Orange degradation, was obtained with the Ru-modified ZnO photocatalyst at 0.25 mol% Ru loading. In particular, after four hours of UV irradiation time, the discoloration and mineralization degree were equal to 83% and 78%, with a simultaneous hydrogen production of 1216 µmol L−1. This result demonstrates the ability of the photocatalytic process to valorize a dye present in wastewater, managing to obtain a hydrogen production comparable with the data present in the literature today in the presence of other sacrificial substances. Full article
(This article belongs to the Section Photocatalysis)
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Article
Preparation of Chloromethylated Pitch–Based Hyper–Crosslinked Polymers and An Immobilized Acidic Ionic Liquid as A Catalyst for the Synthesis of Biodiesel
Catalysts 2019, 9(11), 963; https://doi.org/10.3390/catal9110963 - 15 Nov 2019
Cited by 3 | Viewed by 967
Abstract
Hyper-crosslinking polymers and its immobilized acid ionic liquid catalyst were prepared using cheap pitch, as a monomer, through hyper-crosslinking reactions and allyl chloride, as a chlorine source, for chloromethylation and further grafting with imidazole and functionalizing with sulfonic acid. The polymers were characterized [...] Read more.
Hyper-crosslinking polymers and its immobilized acid ionic liquid catalyst were prepared using cheap pitch, as a monomer, through hyper-crosslinking reactions and allyl chloride, as a chlorine source, for chloromethylation and further grafting with imidazole and functionalizing with sulfonic acid. The polymers were characterized by FE-SEM, FTIR, TG, and nitrogen sorption. The grafting ratios of the chloromethylated pitch-based hyper-crosslinked polymer (HCPpitch–CH2–Cl) and immobilized acid ionic liquid [HCPpitch–Im–Pros][Tos] were 3.5 mmol/g and 3.0 mmol/g, and the BET specific surface areas were 520 m2/g and 380 m2/g, respectively. This strategy provides an easy approach to preparing highly stable and acid functionalized mesoporous catalysts. The immobilized acidic ionic liquid was used as a catalyst for the esterification of oleic acid and methanol to synthesize biodiesel. The results demonstrated that under the optimal conditions of an alcohol to acid molar ratio of 7:1, ionic liquid to oleic acid molar ratio of 0.12, and a reaction time of 3 h at atmospheric pressure, the yield of methyl oleate can reach up to 93%. Moreover, the catalyst was reused five times without the yield decreasing significantly. This study shows that [HCPpitch–Im–Pros][Tos] is a robust catalyst for the synthesis of biodiesel. Full article
(This article belongs to the Section Catalytic Materials)
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Review
Clostridium sp. as Bio-Catalyst for Fuels and Chemicals Production in a Biorefinery Context
Catalysts 2019, 9(11), 962; https://doi.org/10.3390/catal9110962 - 15 Nov 2019
Cited by 5 | Viewed by 1430
Abstract
Clostridium sp. is a genus of anaerobic bacteria capable of metabolizing several substrates (monoglycerides, diglycerides, glycerol, carbon monoxide, cellulose, and more), into valuable products. Biofuels, such as ethanol and butanol, and several chemicals, such as acetone, 1,3-propanediol, and butyric acid, can be produced [...] Read more.
Clostridium sp. is a genus of anaerobic bacteria capable of metabolizing several substrates (monoglycerides, diglycerides, glycerol, carbon monoxide, cellulose, and more), into valuable products. Biofuels, such as ethanol and butanol, and several chemicals, such as acetone, 1,3-propanediol, and butyric acid, can be produced by these organisms through fermentation processes. Among the most well-known species, Clostridium carboxidivorans, C. ragsdalei, and C. ljungdahlii can be highlighted for their ability to use gaseous feedstocks (as syngas), obtained from the gasification or pyrolysis of waste material, to produce ethanol and butanol. C. beijerinckii is an important species for the production of isopropanol and butanol, with the advantage of using hydrolysate lignocellulosic material, which is produced in large amounts by first-generation ethanol industries. High yields of 1,3 propanediol by C. butyricum are reported with the use of another by-product from fuel industries, glycerol. In this context, several Clostridium wild species are good candidates to be used as biocatalysts in biochemical or hybrid processes. In this review, literature data showing the technical viability of these processes are presented, evidencing the opportunity to investigate them in a biorefinery context. Full article
(This article belongs to the Special Issue Catalytic Biomass to Renewable Biofuels and Biomaterials)
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Article
Truncated Prosequence of Rhizopus oryzae Lipase: Key Factor for Production Improvement and Biocatalyst Stability
Catalysts 2019, 9(11), 961; https://doi.org/10.3390/catal9110961 - 15 Nov 2019
Cited by 4 | Viewed by 1377
Abstract
Recombinant Rhizopus oryzae lipase (mature sequence, rROL) was modified by adding to its N-terminal 28 additional amino acids from the C-terminal of the prosequence (proROL) to obtain a biocatalyst more suitable for the biodiesel industry. Both enzymes were expressed in Pichia pastoris and [...] Read more.
Recombinant Rhizopus oryzae lipase (mature sequence, rROL) was modified by adding to its N-terminal 28 additional amino acids from the C-terminal of the prosequence (proROL) to obtain a biocatalyst more suitable for the biodiesel industry. Both enzymes were expressed in Pichia pastoris and compared in terms of production bioprocess parameters, biochemical properties, and stability. Growth kinetics, production, and yields were better for proROL harboring strain than rROL one in batch cultures. When different fed-batch strategies were applied, lipase production and volumetric productivity of proROL-strain were always higher (5.4 and 4.4-fold, respectively) in the best case. rROL and proROL enzymatic activity was dependent on ionic strength and peaked in 200 mM Tris-HCl buffer. The optimum temperature and pH for rROL were influenced by ionic strength, but those for proROL were not. The presence of these amino acids altered lipase substrate specificity and increased proROL stability when different temperature, pH, and methanol/ethanol concentrations were employed. The 28 amino acids were found to be preferably removed by proteases, leading to the transformation of proROL into rROL. Nevertheless, the truncated prosequence enhanced Rhizopus oryzae lipase heterologous production and stability, making it more appropriate as industrial biocatalyst. Full article
(This article belongs to the Special Issue Solid Acid Catalysts for Biodiesel Production)
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Communication
Ionic, Core-Corona Polymer Microsphere-Immobilized MacMillan Catalyst for Asymmetric Diels-Alder Reaction
Catalysts 2019, 9(11), 960; https://doi.org/10.3390/catal9110960 - 15 Nov 2019
Cited by 1 | Viewed by 1447
Abstract
The improvement of the catalytic activity of a heterogeneous chiral catalyst is one of the most critical issues, as are its recovery and reuse. The design of a heterogeneous chiral catalyst, including the immobilization method and the support polymer, is of significance for [...] Read more.
The improvement of the catalytic activity of a heterogeneous chiral catalyst is one of the most critical issues, as are its recovery and reuse. The design of a heterogeneous chiral catalyst, including the immobilization method and the support polymer, is of significance for the catalytic activity in asymmetric reactions. An ionic, core-corona polymer microsphere-immobilized MacMillan catalyst (ICCC) was successfully synthesized by the neutralization reaction of sulfonic acid functionalized core-corona polymer microsphere (CCM–SO3H) with a chiral imidazolidinone precursor. We selected the core-corona polymer microsphere as the polymer support for the improvement of catalytic activity and recovery. The MacMillan catalyst was immobilized onto the pendant position of the corona with ionic bonding. ICCC exhibited excellent enantioselectivity up to 92% enantiomeric excess (ee) (exo) and >99% ee (endo) in the asymmetric Diels-Alder (DA) reaction of (E)-cinnamaldehyde and 1,3-cyclopentadiene. ICCC was quantitatively recovered by centrifugation because of the microsphere structure. The recovered ICCC was reused without significant loss of the enantioselectivity. Full article
(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)
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Article
The Potential Applications of Bacillus sp. and Pseudomonas sp. Strains with Antimicrobial Activity against Phytopathogens, in Waste Oils and the Bioremediation of Hydrocarbons
Catalysts 2019, 9(11), 959; https://doi.org/10.3390/catal9110959 - 15 Nov 2019
Cited by 2 | Viewed by 805
Abstract
Biodegradation is one of the primary mechanisms for the elimination of petroleum and other hydrocarbon pollutants from the environment. This study presents the results obtained with two newly isolated microorganisms and their potential applications in bioremediation, agriculture, and industrial fields. Twenty-five strains of [...] Read more.
Biodegradation is one of the primary mechanisms for the elimination of petroleum and other hydrocarbon pollutants from the environment. This study presents the results obtained with two newly isolated microorganisms and their potential applications in bioremediation, agriculture, and industrial fields. Twenty-five strains of microorganisms were isolated from plant materials and were subject to a selection process on the basis of antimicrobial activity. Two bacterial strains, respectively Bacillus mycoides (Bm) and Pseudomonas putida (B1), were selected for further experiments, based on the largest inhibition zones against the phytopathogens Erwinia carotovora and Xanthomonas campestris. The production of biosurfactants and enzymes was evaluated in specific media. In order to assess the production of biosurfactants, submerged bioprocesses were carried out on Yeast Malt Peptone Glucose (YMPG), M44, Luria-Bertani (LB), and King B media (KB); the supernatants were used to form emulsions with heptane, octane, and sunflower oil, and the emulsifying indices were determined. Full article
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Article
Highly Selective pH-Dependent Ozonation of Cyclohexane over Mn/γ-Al2O3 Catalysts at Ambient Reaction Conditions
Catalysts 2019, 9(11), 958; https://doi.org/10.3390/catal9110958 - 15 Nov 2019
Cited by 1 | Viewed by 942
Abstract
The selective oxidation of cyclohexane to a mixture of cyclohexanol and cyclohexanone (KA oil) is one of the imperative reactions in industrial processes. In this study, the catalytic performance of manganese-supported gamma alumina (Mn/γ-Al2O3) catalysts is investigated in the [...] Read more.
The selective oxidation of cyclohexane to a mixture of cyclohexanol and cyclohexanone (KA oil) is one of the imperative reactions in industrial processes. In this study, the catalytic performance of manganese-supported gamma alumina (Mn/γ-Al2O3) catalysts is investigated in the selective oxidation of cyclohexane at ambient conditions using ozone. The catalysts were prepared by the wet impregnation method, and their physio-chemical properties were studied by Fourier Transform Infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) spectroscopy, Scanning Electron Microscopy-Energy Dispersive X-ray spectroscopy (SEM-EDX), Transmission Electron Microscopy (TEM), Inductively Coupled Plasma (ICP) spectroscopy, and Brunauer Emmett and Teller (BET). The reaction conditions were optimised considering various parameters such as reaction time, pH, and various percentages of the manganese supported in gamma alumina. The oxidation of cyclohexane was conducted in an impinger reactor unit at pH 3, 7, and 11 for 1 h of ozonation time. The aliquots were collected after 30 min and 1 h of ozonation time and analysed with GC-MS and FT-IR spectroscopy. The 2.5% Mn/γ-Al2O3 catalyst exhibited a significantly enhanced catalytic performance at pH 3 and 7 with a percentage conversion of 9% and 15% at pH 3 and 7, respectively, after 30 min of ozonation time. However, after 1 h of ozonation time, the percentage conversions were increased to 23% and 29% at pH 3 and 7, respectively. At pH 11, 5% Mn/γ-Al2O3 exhibit high catalytic performance with a percentage conversion of 19% and 31% after 30 minutes and 1 h of ozonation time, respectively. The percentage selectivity obtained is 100% toward KA oil and/or cyclohexanone depending on pH and reaction time. Full article
(This article belongs to the Section Nanostructured Catalysts)
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Article
Developmental Study of Soot-Oxidation Catalysts for Fireplaces: The Effect of Binder and Preparation Techniques on Catalyst Texture and Activity
Catalysts 2019, 9(11), 957; https://doi.org/10.3390/catal9110957 - 15 Nov 2019
Cited by 2 | Viewed by 838
Abstract
An awareness of increasing climate and health problems has driven the development of new functional and affordable soot-oxidation catalysts for stationary sources, such as fireplaces. In this study, Al(OH)3, water glass and acidic aluminium phosphate binder materials were mixed with soot-oxidation [...] Read more.
An awareness of increasing climate and health problems has driven the development of new functional and affordable soot-oxidation catalysts for stationary sources, such as fireplaces. In this study, Al(OH)3, water glass and acidic aluminium phosphate binder materials were mixed with soot-oxidation catalysts. The effect of the binder on the performance of the Ag/La-Al2O3 catalyst was examined, while the Pt/La-Al2O3 catalyst bound with Al(OH)3 was used as a reference. Soot was oxidised above 340 °C on the Ag/La-Al2O3 catalyst, but at 310 °C with same catalyst bound with Al(OH)3. The addition of water glass decreased the catalytic performance because large silver crystals and agglomeration resulted in a blockage of the support material’s pores. Pt/La-Al2O3 bound with Al(OH)3 was ineffective in a fireplace environment. We believe that AgOx is the active form of silver in the catalyst. Hence, Ag/La-Al2O3 was shown to be compatible with the Al(OH)3 binder as an effective catalyst for fireplace soot oxidation. Full article
(This article belongs to the Special Issue Catalytic Combustion of Soot)
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Article
Low-Temperature Selective Catalytic Reduction of NO with NH3 over Natural Iron Ore Catalyst
Catalysts 2019, 9(11), 956; https://doi.org/10.3390/catal9110956 - 14 Nov 2019
Cited by 7 | Viewed by 834
Abstract
The selective catalytic reduction of NO with NH3 at low temperatures has been investigated with natural iron ore catalysts. Four iron ore raw materials from different locations were taken and processed to be used as catalysts. The methods of X-ray diffraction (XRD), [...] Read more.
The selective catalytic reduction of NO with NH3 at low temperatures has been investigated with natural iron ore catalysts. Four iron ore raw materials from different locations were taken and processed to be used as catalysts. The methods of X-ray diffraction (XRD), X-ray fluorescence (XRF), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), ammonia temperature-programmed desorption (NH3-TPD), scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR) were used to characterize the materials. The results showed that the sample A (comprised mainly of α-Fe2O3 and γ-Fe2O3), calcined at 250 °C, achieved excellent selective catalytic reduction (SCR) activity (above 80% at 170–350 °C) and N2 selectivity (above 90% up to 250 °C) at low temperatures. Suitable calcination temperature, large surface area, high concentration of surface-adsorbed oxygen, good reducibility, lots of acid sites and adsorption of the reactants were responsible for the excellent SCR performance of the iron ore. However, the addition of H2O and SO2 in the feed gas showed some adverse effects on the SCR activity. The FT-IR analysis indicated the formation of sulfate salts on the surface of the catalyst during the SCR reaction in the presence of SO2, which could cause pore plugging and result in the suppression of the catalytic activity. Full article
(This article belongs to the Special Issue Sustainable and Environmental Catalysis)
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Article
Gold(I) Complexes with Ferrocenylphosphino Sulfonate Ligands: Synthesis and Application in the Catalytic Addition of Carboxylic Acids to Internal Alkynes in Water
Catalysts 2019, 9(11), 955; https://doi.org/10.3390/catal9110955 - 14 Nov 2019
Cited by 3 | Viewed by 1012
Abstract
The synthesis and characterization of novel gold(I) complexes containing hydrophilic ferrocenylphosphino sulfonate ligands, i.e., compounds [AuCl{(η5-C5H3PR2(SO3iPr))Fe(η5-C5H5)}] (R = Ph (2a), p-Tol [...] Read more.
The synthesis and characterization of novel gold(I) complexes containing hydrophilic ferrocenylphosphino sulfonate ligands, i.e., compounds [AuCl{(η5-C5H3PR2(SO3iPr))Fe(η5-C5H5)}] (R = Ph (2a), p-Tol (2b), Cy (2c)), are presented, including a single-crystal X-ray diffraction study on 2a. Complexes 2ac were checked as catalysts for the intermolecular addition of carboxylic acids to nonactivated internal alkynes using water as a green reaction medium. The best results in terms of activity were obtained with 2a in combination with AgOAc, which was able to promote the selective anti addition of a variety of aromatic, aliphatic, and α,β-unsaturated carboxylic acids to both symmetrical and unsymmetrical internal alkynes at 60 °C, employing metal loadings of only 2 mol %. Full article
(This article belongs to the Special Issue Advances in Green Catalysis for Sustainable Organic Synthesis)
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Article
Nitrogen and Cobalt Co-Coped Carbon Materials Derived from Biomass Chitin as High-Performance Electrocatalyst for Aluminum-Air Batteries
Catalysts 2019, 9(11), 954; https://doi.org/10.3390/catal9110954 - 14 Nov 2019
Cited by 9 | Viewed by 929
Abstract
Development of convenient, economic electrocatalysts for oxygen reduction reaction (ORR) in alkaline medium is of great significance to practical applications of aluminum-air batteries. Herein, a biomass chitin-derived carbon material with high ORR activities has been prepared and applied as electrocatalysts in Al-air batteries. [...] Read more.
Development of convenient, economic electrocatalysts for oxygen reduction reaction (ORR) in alkaline medium is of great significance to practical applications of aluminum-air batteries. Herein, a biomass chitin-derived carbon material with high ORR activities has been prepared and applied as electrocatalysts in Al-air batteries. The obtained cobalt, nitrogen co-doped carbon material (CoNC) exhibits the positive onset potential 0.86 V vs. RHE (reversible hydrogen electrode) and high-limiting current density 5.94 mA cm−2. Additionally, the durability of the CoNC material in alkaline electrolyte shows better stability when compared to the commercial Pt/C catalyst. Furthermore, the Al-air battery using CoNC as an air cathode catalyst provides the power density of 32.24 mW cm−2 and remains the constant discharge voltage of 1.17 V at 20 mA cm−2. This work not only provides a facile method to synthesize low-cost and efficient ORR electrocatalysts for Al-air batteries, but also paves a new way to explore and utilize high-valued biomass materials. Full article
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Article
Study on the Catalytic Pyrolysis Mechanism of Lignite by Using Extracts as Model Compounds
Catalysts 2019, 9(11), 953; https://doi.org/10.3390/catal9110953 - 14 Nov 2019
Viewed by 557
Abstract
Understanding the catalytic pyrolysis mechanism of lignite is of great significance for obtaining a high yield of the target products or designing high-efficiency catalysts, which are generally derived by using simple model compounds, while the ordinary model compounds cannot represent the real atmosphere [...] Read more.
Understanding the catalytic pyrolysis mechanism of lignite is of great significance for obtaining a high yield of the target products or designing high-efficiency catalysts, which are generally derived by using simple model compounds, while the ordinary model compounds cannot represent the real atmosphere of lignite pyrolysis owing to the simple structures and single reactions. Based on the coal two-phase model, the extractable compounds are the important compositions of coal, which can reflect the partial characteristics of raw coal while obtaining a high extraction yield. Hence, a better understanding of the interaction between the coal structure and catalyst can be inferred by using a mobile phase in coal as model compounds instead of conventional simple compounds. In this work, tetrahydrofuran extracts of lignite were chosen as model compounds to study the catalytic pyrolysis mechanism with separate addition of Fe(NO3)3 and FeCl3 by using a thermogravimetric combined with mass spectrometry. It was found that about 77.88% of the extracts were vaporized before 700 °C, and the residual yield was 22.12%. With the separate addition of 5 wt % of Fe(NO3)3 and FeCl3, the conversion of the extracts increased to 84.38% and 89.66%. Meanwhile, the final temperature decreased to 650 and 550 °C, respectively. The addition of Fe(NO3)3 and FeCl3 promoted the breakage of aliphatic chains at approximately 150 °C, leading to the generation of CH4 and H2 in the temperature range 100–200 °C, which were nearly invisible for that without catalyst. The addition of iron-based catalysts allowed more CO2 formation at approximately 200 °C since they enabled efficient promotion of the cleavage of carboxyl functionals at lower temperatures. The enlarged peak of H2O and CH4 at approximately 500 °C means that iron-based catalysts are significant for the cleavage of methoxy groups in the catalytic respect. Aromatic side chains facilitated cracking at approximately 500 °C, leading to more light aliphatics and aromatics generation in this temperature range. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Article
Performance of a Ni-Cu-Co/Al2O3 Catalyst on in-situ Hydrodeoxygenation of Bio-derived Phenol
Catalysts 2019, 9(11), 952; https://doi.org/10.3390/catal9110952 - 14 Nov 2019
Cited by 4 | Viewed by 974
Abstract
The in-situ hydrodeoxygenation of bio-derived phenol is an attractive routine for upgrading bio-oils. Herein, an active trimetallic Ni-Cu-Co/Al2O3 catalyst was prepared and applied in the in-situ hydrodeoxygenation of bio-derived phenol. Comparison with the monometallic Ni/Al2O3 catalyst and [...] Read more.
The in-situ hydrodeoxygenation of bio-derived phenol is an attractive routine for upgrading bio-oils. Herein, an active trimetallic Ni-Cu-Co/Al2O3 catalyst was prepared and applied in the in-situ hydrodeoxygenation of bio-derived phenol. Comparison with the monometallic Ni/Al2O3 catalyst and the bimetallic Ni-Co/Al2O3 and Ni-Cu/Al2O3 catalysts, the Ni-Cu-Co/Al2O3 catalyst exhibited the highest catalytic activity because of the formation of Ni-Cu-Co alloy on the catalyst characterized by using X-ray powder diffraction (XRD), temperature programmed reduction (TPR), N2 physisorption, scanning electron microscope (SEM), and transmission electron microscope (TEM). The phenol conversion of 100% and the cyclohexane yield of 98.3% could be achieved in the in-situ hydrodeoxygenation of phenol at 240 °C and 4 MPa N2 for 6 h. The synergistic effects of Ni with Cu and Co of the trimetallic Ni-Cu-Co/Al2O3 catalyst played a significant role in the in-situ hydrodeoxygenation process of phenol, which not only had a positive effect on the production of hydrogen but also owned an excellent hydrogenolysis activity to accelerate the conversion of cyclohexanol to cyclohexane. Furthermore, the catalyst also exhibited excellent recyclability and good potential for the upgrading of bio-oils. Full article
(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)
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Article
Novel Cobalt Complex as an Efficient Catalyst for Converting CO2 into Cyclic Carbonates under Mild Conditions
Catalysts 2019, 9(11), 951; https://doi.org/10.3390/catal9110951 - 14 Nov 2019
Cited by 2 | Viewed by 705
Abstract
Based on the ligand H2dpPzda (1), a novel cobalt complex [Co(H2dpPzda)(NCS)2]·CH3OH(2) has been synthesized and characterized. The Complex 2 exhibited excellent catalytic performance for converting CO2 into cyclic carbonates under [...] Read more.
Based on the ligand H2dpPzda (1), a novel cobalt complex [Co(H2dpPzda)(NCS)2]·CH3OH(2) has been synthesized and characterized. The Complex 2 exhibited excellent catalytic performance for converting CO2 into cyclic carbonates under mild conditions. For propylene oxide (PO) and CO2 synthesis of propylene carbonate (PC), the catalytic system showed a remarkable TOF as high as 29,200 h−1. The catalytic system also showed broad substrate scope of epoxide. Additionally, the catalyst could be recycled to maintain the integrity of the structure and remained equal to the level of its catalytic activity even after seven catalytic rounds. Additionally, a possible catalytic mechanism was proposed due to the high catalytic activity which might be owing to the synergism of Lewis acidic metal centers and N group. Full article
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Article
In-Situ Arc Discharge-Derived FeSn2/Onion-Like Carbon Nanocapsules as Improved Stannide-Based Electrocatalytic Anode Materials for Lithium-Ion Batteries
Catalysts 2019, 9(11), 950; https://doi.org/10.3390/catal9110950 - 13 Nov 2019
Cited by 1 | Viewed by 804
Abstract
Core/shell-structured FeSn2/onion-like carbon (FeSn2/OLC) nanocapsules of confined size range of sub-50 nm are synthesized via an in-situ arc-discharge process, and are evaluated in comparison with FeSn2 nanoparticles as an improved stannide-based electrocatalytic anode material for Li-ion batteries (LIBs). [...] Read more.
Core/shell-structured FeSn2/onion-like carbon (FeSn2/OLC) nanocapsules of confined size range of sub-50 nm are synthesized via an in-situ arc-discharge process, and are evaluated in comparison with FeSn2 nanoparticles as an improved stannide-based electrocatalytic anode material for Li-ion batteries (LIBs). The in-situ arc-discharge process allows a facile one-pot procedure for forming crystalline FeSn2 stannide alloy nanoparticle cores coated by defective OLC thin shells in addition to a confined crystal growth of the FeSn2 nanoparticle cores. The LIB cells assembled using the FeSn2/OLC nanocapsules as the electrocatalytic anodes exhibit superior full specific discharge capacity of 519 mAh·g−1 and specific discharge capacity retention of ~62.1% after 100 charge-discharge cycles at 50 mA·g−1 specific current. The electrochemical stability of FeSn2/OLC nanocapsules is demonstrated from the good cycle stability of the LIBs with a high specific discharge capacity retention of 67.5% on a drastic change in specific current from 4000 to 50 mA·g−1. A formation mechanism is proposed to describe the confined crystal growth of the FeSn2 nanoparticle cores and the formation of the FeSn2/OLC core/shell structure. The observed electrochemical performance enhancement is ascribed to the synergetic effects of the enabling of a reversible lithiation process during charge-discharge of the LIB cells by the FeSn2 nanoparticle cores as well as the protection of the FeSn2 nanoparticle cores from volume change-induced pulverization and solid electrolyte interphase-induced passivation by the OLC shells. Full article
(This article belongs to the Special Issue Metal Nanomaterials for Electrocatalysis)
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Article
The Sonophotocatalytic Degradation of Pharmaceuticals in Water by MnOx-TiO2 Systems with Tuned Band-Gaps
Catalysts 2019, 9(11), 949; https://doi.org/10.3390/catal9110949 - 12 Nov 2019
Cited by 15 | Viewed by 868
Abstract
Advanced oxidation processes (AOPs) are technologies to degrade organic pollutants to carbon dioxide and water with an eco-friendly approach to form reactive hydroxyl radicals. Photocatalysis is an AOP whereby TiO2 is the most adopted photocatalyst. However, TiO2 features a wide (3.2 [...] Read more.
Advanced oxidation processes (AOPs) are technologies to degrade organic pollutants to carbon dioxide and water with an eco-friendly approach to form reactive hydroxyl radicals. Photocatalysis is an AOP whereby TiO2 is the most adopted photocatalyst. However, TiO2 features a wide (3.2 eV) and fast electron-hole recombination. When Mn is embedded in TiO2, it shifts the absorption wavelength towards the visible region of light, making it active for natural light applications. We present a systematic study of how the textural and optical properties of Mn-doped TiO2 vary with ultrasound applied during synthesis. We varied ultrasound power, pulse length, and power density (by changing the amount of solvent). Ultrasound produced mesoporous MnOx-TiO2 powders with a higher surface area (101–158 m2 g−1), pore volume (0-13–0.29 cc g−1), and smaller particle size (4–10 µm) than those obtained with a conventional sol-gel method (48–129 m2 g−1, 0.14–0.21 cc g−1, 181 µm, respectively). Surprisingly, the catalysts obtained with ultrasound had a content of brookite that was at least 28%, while the traditional sol-gel samples only had 7%. The samples synthesized with ultrasound had a wider distribution of the band-gaps, in the 1.6–1.91 eV range, while traditional ones ranged from 1.72 eV to 1.8 eV. We tested activity in the sonophotocatalytic degradation of two model pollutants (amoxicillin and acetaminophen). The catalysts synthesized with ultrasound were up to 50% more active than the traditional samples. Full article
(This article belongs to the Special Issue Photocatalysis and Environment)
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Article
Facile Synthesis of High Performance Iron Oxide/Carbon Nanocatalysts Derived from the Calcination of Ferrocenium for the Decomposition of Methylene Blue
Catalysts 2019, 9(11), 948; https://doi.org/10.3390/catal9110948 - 12 Nov 2019
Cited by 1 | Viewed by 794
Abstract
Iron oxide/carbon nanocatalysts were successfully synthesized by the calcination of ferrocenium at high temperatures ranging from 500 to 900 °C. Then the synthesized nanocomposites were characterized by XRD (X-Ray Diffraction), TEM (Transmission Electron Microscopy), VSM (Vibrating-Sample Magnetometry), BET (Brunauer-Emmett-Teller surface area measurements), TGA [...] Read more.
Iron oxide/carbon nanocatalysts were successfully synthesized by the calcination of ferrocenium at high temperatures ranging from 500 to 900 °C. Then the synthesized nanocomposites were characterized by XRD (X-Ray Diffraction), TEM (Transmission Electron Microscopy), VSM (Vibrating-Sample Magnetometry), BET (Brunauer-Emmett-Teller surface area measurements), TGA (Thermogravimetric Analysis), XPS (X-Ray Photoelectron Spectroscopy), EPR (Electron Paramagnetic Resonance), and CHN elemental analysis. The prepared nanocatalysts were applied for the decomposition of methylene blue as a model in wastewater treatment. It was unexpected to discover that the prepared nanocatalysts were highly active for the reaction with methylene blue in the dark even though no excess of hydrogen peroxide was added. The nanocatalyst calcined at 800 °C exhibited the rod shape with the best catalytic activity. The nanocatalysts could be reused for 12 times without the significant loss of the catalytic activity. Full article
(This article belongs to the Special Issue Catalysis and Fine Chemicals)
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Article
{CeO2/Bi2Mo1−xRuxO6} and {Au/Bi2Mo1−xRuxO6} Catalysts for Low-Temperature CO Oxidation
Catalysts 2019, 9(11), 947; https://doi.org/10.3390/catal9110947 - 12 Nov 2019
Cited by 3 | Viewed by 744
Abstract
Nowadays, one of the most important challenges that humanity faces is to find alternative ways of reducing pollutant emissions. CeO2/Bi2Mo1−xRuxO6 and Au/Bi2Mo1−xRuxO6 catalysts were prepared to efficiently [...] Read more.
Nowadays, one of the most important challenges that humanity faces is to find alternative ways of reducing pollutant emissions. CeO2/Bi2Mo1−xRuxO6 and Au/Bi2Mo1−xRuxO6 catalysts were prepared to efficiently transform carbon monoxide (CO) to carbon dioxide (CO2) at low temperatures. The systems were prepared in a two-step process. First, Bi2Mo1−xRuxO6 supports were synthesized through the hydrothermal procedure under microwave heating. Then, CeO2 was deposited on Bi2Mo1−xRuxO6 using the wet impregnation method, while the incipient impregnation method was selected to deposit gold nanoparticles. The CeO2/Bi2Mo1−xRuxO6 and Au/Bi2Mo1−xRuxO6 catalysts were characterized using SEM microscopy and XRD. Furthermore, energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy were used. Tests were carried out for the supported catalysts in CO oxidation, and high conversion values, nearing 100%, was observed in a temperature range of 100 to 250 °C. The results showed that the best system was the Au/Bi2Mo0.95Ru0.05O6 catalyst, with CO oxidation starting at 50 °C and reaching 100% conversion at 186 °C. Full article
(This article belongs to the Special Issue Catalysis for the Removal of Gas-Phase Pollutants)
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Article
Kinetic Monte-Carlo Simulation of Methane Steam Reforming over a Nickel Surface
Catalysts 2019, 9(11), 946; https://doi.org/10.3390/catal9110946 - 11 Nov 2019
Cited by 2 | Viewed by 1007
Abstract
A kinetic Monte-Carlo model was developed in order to simulate the methane steam reforming and kinetic behavior of this reaction. There were 34 elementary step reactions that were used, based on the Langmuir–Hinshelwood mechanism, over a nickel catalyst. The simulation was investigated at [...] Read more.
A kinetic Monte-Carlo model was developed in order to simulate the methane steam reforming and kinetic behavior of this reaction. There were 34 elementary step reactions that were used, based on the Langmuir–Hinshelwood mechanism, over a nickel catalyst. The simulation was investigated at a mole fraction of methane between 0.1 and 0.9, temperature of 600 to 1123 K, and total pressure of up to 40 bar. The simulated results were collected at a steady state and were compared with the previously reported experiments. The fractional coverages of the adsorbed species and the production rates of H2, CO, and CO2 were evaluated, and the effects of the reaction temperature, feed concentration, and total pressure of reactants were also investigated. The simulation results showed a similar trend with previous experimental results, and suggested the appropriate conditions for this reaction, which were a total pressure of 10 bar, with the mole fraction of methane in a range of 0.4–0.5. Full article
(This article belongs to the Special Issue Catalysis and Fine Chemicals)
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Article
Irrigation Combined with Aeration Promoted Soil Respiration through Increasing Soil Microbes, Enzymes, and Crop Growth in Tomato Fields
Catalysts 2019, 9(11), 945; https://doi.org/10.3390/catal9110945 - 11 Nov 2019
Cited by 3 | Viewed by 712
Abstract
Soil respiration (Rs) is one of the major components controlling the carbon budget of terrestrial ecosystems. Aerated irrigation has been proven to increase Rs compared with the control, but the mechanisms of CO2 release remain poorly understood. The objective of this study [...] Read more.
Soil respiration (Rs) is one of the major components controlling the carbon budget of terrestrial ecosystems. Aerated irrigation has been proven to increase Rs compared with the control, but the mechanisms of CO2 release remain poorly understood. The objective of this study was (1) to test the effects of irrigation, aeration, and their interaction on Rs, soil physical and biotic properties (soil water-filled pore space, temperature, bacteria, fungi, actinomycetes, microbial biomass carbon, cellulose activity, dehydrogenase activity, root morphology, and dry biomass of tomato), and (2) to assess how soil physical and biotic variables control Rs. Therefore, three irrigation levels were included (60%, 80%, and 100% of full irrigation). Each irrigation level contained aeration and control. A total of six treatments were included. The results showed that aeration significantly increased total root length, dry biomass of leaf, stem, and fruit compared with the control (p < 0.05). The positive effect of irrigation on dry biomass of leaf, fruit, and root was significant (p < 0.05). With respect to the control, greater Rs under aeration (averaging 6.2% increase) was mainly driven by soil water-filled pore space, soil bacteria, and soil fungi. The results of this study are helpful for understanding the mechanisms of soil CO2 release under aerated subsurface drip irrigation. Full article
(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)
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Article
Ni/NiO Nanocomposites with Rich Oxygen Vacancies as High-Performance Catalysts for Nitrophenol Hydrogenation
Catalysts 2019, 9(11), 944; https://doi.org/10.3390/catal9110944 - 11 Nov 2019
Cited by 2 | Viewed by 872
Abstract
Heterogeneous catalysis often involves charge transfer between adsorbed molecules and the surface of catalyst, and thus their activity depends on the surface charge density. The efficiency of charge transfer could be optimized by adjusting the concentration of oxygen vacancies (Ov). In [...] Read more.
Heterogeneous catalysis often involves charge transfer between adsorbed molecules and the surface of catalyst, and thus their activity depends on the surface charge density. The efficiency of charge transfer could be optimized by adjusting the concentration of oxygen vacancies (Ov). In this work, hexagonal Ni(OH)2 nanoparticles were initially synthesized by a hydrothermal process using aluminum powder as the sacrificial agent, and were then converted into 2D Ni/NiO nanocomposites through in situ reduction in hydrogen flow. The oxygen vacancy concentration in the NiO nanosheet could be well-controlled by adjusting the reduction temperature. This resulted in strikingly high activities for hydrogenation of nitrophenol. The Ni/NiO nanocomposite could easily be recovered by a magnetic field for reuse. The present finding is beneficial for producing better hydrogenation catalysts and paves the way for the design of highly efficient catalysts. Full article
(This article belongs to the Section Nanostructured Catalysts)
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Article
Novel Functionality of Lithium-Impregnated Titania as Nanocatalyst
Catalysts 2019, 9(11), 943; https://doi.org/10.3390/catal9110943 - 09 Nov 2019
Viewed by 707
Abstract
The present work incorporates the synthesis of a multifunctional catalyst for the transesterification of waste cooking oil (WCO) to biodiesel and recovery of rare earth elements (REEs). For this purpose, TiO2 nanoparticles and TiO2 doped with lithium ions were prepared. The [...] Read more.
The present work incorporates the synthesis of a multifunctional catalyst for the transesterification of waste cooking oil (WCO) to biodiesel and recovery of rare earth elements (REEs). For this purpose, TiO2 nanoparticles and TiO2 doped with lithium ions were prepared. The influence of lithium ions on the catalytic performance of TiO2 was attained by impregnation of the different molar ratios of lithium hydroxide to bare TiO2. Then each catalyst was screened for catalytic conversion of WCO to fatty acid methyl ester (FAME) and also for REEs recovery. All synthesized materials were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) analysis, and Hammett indicator for the basicity test. The obtained biodiesel was characterized by gas chromatography with mass spectrometry (GC-MS), 1H, and 13C nuclear magnetic resonance (NMR). Moreover, the physical parameters of the synthesized biodiesel were also determined. The REEs recovery efficiency of synthesized nanomaterials was investigated, and the percentage of REEs removal was determined by inductively-coupled plasma optical emission spectroscopy (ICP-OES). Full article
(This article belongs to the Special Issue Fuel Processing with Multifunctional Catalysts)
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Article
Synthesis of Tri- and Disubstituted Fluorenols and Derivatives Thereof Using Catalytic [2+2+2] Cyclotrimerization
Catalysts 2019, 9(11), 942; https://doi.org/10.3390/catal9110942 - 09 Nov 2019
Cited by 2 | Viewed by 974
Abstract
A method for regioselective synthesis of 2,4-disubstituted and more highly substituted fluorenols using catalytic [2+2+2]cyclotrimerization of mono- and disubstituted diynes with terminal alkynes was explored. In the former case, the preferential formation of the 2,4-regioisomers was achieved in the presence of Cp*Ru(cod)Cl, whereas [...] Read more.
A method for regioselective synthesis of 2,4-disubstituted and more highly substituted fluorenols using catalytic [2+2+2]cyclotrimerization of mono- and disubstituted diynes with terminal alkynes was explored. In the former case, the preferential formation of the 2,4-regioisomers was achieved in the presence of Cp*Ru(cod)Cl, whereas Rh-based catalysts tended to provide 3,4-regioisomers as the major products. The 2,4-disubstituted fluorenols were converted into the corresponding 9,9′-spirobifluorene derivatives and their structural and photophysical properties were evaluated. Full article
(This article belongs to the Special Issue Transition-Metal-Catalyzed Reactions in Organic Synthesis)
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