Catalytic Oxidation of Hydrocarbons

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (20 January 2022) | Viewed by 30494

Special Issue Editor

Special Issue Information

Dear Colleagues,

Selective oxidation processes are used to activate raw materials and transform them into useful products and chemical intermediates. Hydrocarbons, in particular alkanes, are the main components of gas and oil and are a good example of such raw materials. The C–H bond(s) of these compounds can be transformed into C–OH or C=O groups that will lead to the production of high added value products with applications in fine chemistry. The selective oxidation of hydrocarbons is a very important reaction taking place in industrial processes based on petroleum, since the oxygenated compounds produced can be used as intermediates for organic synthesis. However, the activation of such bonds remains a challenge for researchers. Reactions are often characterized by low conversions and the formation of unwanted by-products.

The aim of this Special Issue is to cover the oxidations of those substrates, using different catalysts, such as supported nanoparticles, carbon materials, metal oxides, zeolites, and metal organic frameworks, among others. New methods of catalyst preparation and the use of “greener” milder reaction conditions are especially welcome, but we aim at publishing any other recent updates on this particularly important field.

I invite you all to contribute with your valuable research to this Special Issue.

Prof. Sonia Carabineiro
Guest Editor

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Keywords

  • alkane
  • hydrocarbon
  • oxidation
  • gold
  • carbon
  • metal oxides
  • metal organic frameworks
  • zeolites

Published Papers (12 papers)

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Editorial

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2 pages, 171 KiB  
Editorial
Catalytic Oxidation of Hydrocarbons
Catalysts 2024, 14(2), 111; https://doi.org/10.3390/catal14020111 - 31 Jan 2024
Viewed by 455
Abstract
The catalytic oxidation of hydrocarbons stands at the forefront of sustainable chemical transformations, offering pathways to selectively convert aliphatic and aromatic compounds into valuable oxygenated products [...] Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)

Research

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26 pages, 6913 KiB  
Article
Hydrocarbon Oxidation Depth: H2O2/Cu2Cl4·2DMG/CH3CN System
Catalysts 2022, 12(4), 409; https://doi.org/10.3390/catal12040409 - 07 Apr 2022
Cited by 1 | Viewed by 1833
Abstract
The oxidation of hydrocarbons of different structures under the same conditions is an important stage in the study of the chemical properties of both the hydrocarbons themselves and the oxidation catalysts. In a 50% H2O2/Cu2Cl4·2DMG/CH [...] Read more.
The oxidation of hydrocarbons of different structures under the same conditions is an important stage in the study of the chemical properties of both the hydrocarbons themselves and the oxidation catalysts. In a 50% H2O2/Cu2Cl4·2DMG/CH3CN system, where DMG is dimethylglyoxime (Butane-2,3-dione dioxime), at 50 °C under the same or similar conditions, we oxidized eleven RH hydrocarbons of different structures: mono-, bi- and tri-cyclic, framework and aromatic. To compare the composition of the oxidation products of these hydrocarbons, we introduced a new quantitative characteristic, “distributive oxidation depth D(O), %” and showed the effectiveness of its application. The adiabatic ionization potentials (AIP) and the vertical ionization potentials (VIP) of the molecules of eleven oxidized and related hydrocarbons were calculated using the DFT method in the B3LYP/TZVPP level of theory for comparison with experimental values and correlation with D(O). The same calculations of AIP were made for the molecules of the oxidant, solvent, DMG, related compounds and products. It is shown that component X, which determines the mechanism of oxidation of hydrocarbons RH with AIP(Exp) ≥ AIP(X) = 8.55 ± 0.03 eV, is a trans-DMG molecule. Firstly theoretically estimated experimental values of AIP(trans-DMG) = 8.53 eV and AIP(cis-DMG) = 8.27 eV. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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13 pages, 3051 KiB  
Article
Commercial Gold Complexes Supported on Functionalised Carbon Materials as Efficient Catalysts for the Direct Oxidation of Ethane to Acetic Acid
Catalysts 2022, 12(2), 165; https://doi.org/10.3390/catal12020165 - 28 Jan 2022
Cited by 1 | Viewed by 2262
Abstract
The single-pot efficient oxidation of ethane to acetic acid catalysed by Au(I) or Au(III) compounds, chlorotriphenylphosphinegold(I) (1), chlorotrimethylphosphinegold(I) (2), 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidenegold(I) chloride (3), dichloro(2-pyridinecarboxylato)gold(III) (4), homogenous and supported on different carbon materials: activated carbon (AC), multi-walled [...] Read more.
The single-pot efficient oxidation of ethane to acetic acid catalysed by Au(I) or Au(III) compounds, chlorotriphenylphosphinegold(I) (1), chlorotrimethylphosphinegold(I) (2), 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidenegold(I) chloride (3), dichloro(2-pyridinecarboxylato)gold(III) (4), homogenous and supported on different carbon materials: activated carbon (AC), multi-walled carbon nanotubes (CNT) and carbon xerogel (CX), oxidised with nitric acid followed by treatment with NaOH (-ox-Na), is reported. The reactions were performed in water/acetonitrile. The materials were selective for the production of acetic acid, with no trace of by-products being detected. The best homogenous catalysts were complexes 2 and 3 which showed the highest ethane conversion and an acetic acid yield of ca. 21%, followed by 4 and 1. The heterogenised materials showed much better activity than the homogenous counterparts, with acetic acid yields up to 41.4% for 4@CNT-ox-Na, and remarkable selectivity (with acetic acid being the only product detected). The heterogenised catalysts with the best results were reused up to five cycles, with no significant loss of activity, and maintaining high selectivity for acetic acid. 4@CNT-ox-Na showed not only the best catalytic activity but also the best stability during the recycling runs. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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12 pages, 3904 KiB  
Article
Role of PhOH and Tyrosine in Selective Oxidation of Hydrocarbons
Catalysts 2021, 11(9), 1032; https://doi.org/10.3390/catal11091032 - 26 Aug 2021
Cited by 2 | Viewed by 1562
Abstract
Earlier, we established that nickel or iron heteroligand complexes, which include PhOH (nickel complexes) or tyrosine residue (nickel or iron complexes), are not only hydrocarbon oxidation catalysts (in the case of PhOH), but also simulate the active centers of enzymes (PhOH, tyrosine). The [...] Read more.
Earlier, we established that nickel or iron heteroligand complexes, which include PhOH (nickel complexes) or tyrosine residue (nickel or iron complexes), are not only hydrocarbon oxidation catalysts (in the case of PhOH), but also simulate the active centers of enzymes (PhOH, tyrosine). The AFM method established the self-organization of nickel or iron heteroligand complexes, which included tyrosine residue or PhOH, into supramolecular structures on a modified silicon surface. Supramolecular structures were formed as a result of H-bonds and other non-covalent intermolecular interactions and, to a certain extent, reflected the structures involved in the mechanisms of reactions of homogeneous and enzymatic catalysis. Using the AFM method, we obtained evidence at the model level in favor of the involvement of the tyrosine fragment as one of the possible regulatory factors in the functioning of Ni(Fe)ARD dioxygenases or monooxygenases of the family of cytochrome P450. The principles of actions of these oxygenases were used to create highly efficient catalytic systems for the oxidation of hydrocarbons. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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21 pages, 4182 KiB  
Article
One-Stage Catalytic Oxidation of Adamantane to Tri-, Tetra-, and Penta-Ols
Catalysts 2021, 11(8), 1017; https://doi.org/10.3390/catal11081017 - 23 Aug 2021
Cited by 3 | Viewed by 2277
Abstract
Tertiary tetraols of adamantane (C10H16, Tricyclo[3.3.1.1(3,7)]decan) have been widely used for the synthesis of highly symmetric compounds with unique physical and chemical properties. The methods for one-stage simultaneously selective, deep, and cheap oxidation of adamantane to tetraols of different [...] Read more.
Tertiary tetraols of adamantane (C10H16, Tricyclo[3.3.1.1(3,7)]decan) have been widely used for the synthesis of highly symmetric compounds with unique physical and chemical properties. The methods for one-stage simultaneously selective, deep, and cheap oxidation of adamantane to tetraols of different structures have not yet been developed. In this research, chemically simple, cheap, and environmentally friendly reagents are used and that is the first step in this direction. The conditions, under which the impact of a hydrogen peroxide water solution on adamantane dissolved in acetonitrile results in full conversion of adamantane and formation of a total 72% mixture of its tri-, tetra-, and penta-oxygenated products, predominantly poliols, have been found. Conversion and adamantane oxidation depth are shown to depend on the ratio of components of the water-acetonitrile solution and the method of oxidizer solution introduction when using the dimer form of 1:1 dimethylglyoxime and copper dichloride complex as a catalyst. Under the conditions of mass-spectrometry ionization by electrons (70 eV), fragmentation across three C–C bonds of the molecular ions framework of adamantane tertiary alcohols Ad(OH)n in the range n = 0–4 increases linearly with the rise of n. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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12 pages, 3138 KiB  
Article
Studies of Nickel/Samarium-Doped Ceria for Catalytic Partial Oxidation of Methane and Effect of Oxygen Vacancy
Catalysts 2021, 11(6), 731; https://doi.org/10.3390/catal11060731 - 14 Jun 2021
Cited by 5 | Viewed by 2556
Abstract
We investigated the performance of nickel/samarium-doped ceria (Ni/SDC) nanocatalysts on the catalytic partial oxidation of methane (CPOM). Studies of temperature-programmed surface reaction and reduction reveal that catalytic activity is determined by a synergistic effect produced by Ni metals and metal-support interaction. Catalytic activity [...] Read more.
We investigated the performance of nickel/samarium-doped ceria (Ni/SDC) nanocatalysts on the catalytic partial oxidation of methane (CPOM). Studies of temperature-programmed surface reaction and reduction reveal that catalytic activity is determined by a synergistic effect produced by Ni metals and metal-support interaction. Catalytic activity was more dependent on the Ni content below 600 °C, while there is not much difference for all catalysts at high temperatures. The catalyst exhibiting high activities toward syngas production (i.e., a CH4 conversion >90% at 700 °C) requires a medium Ni-SDC interaction with an Sm/Ce ratio of about 1/9 to 2/8. This is accounted for by optimum oxygen vacancies and adequate ion diffusivity in the SDCs which, as reported, also display the highest ion conductivity for fuel cell applications. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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17 pages, 4540 KiB  
Article
Enhanced Performance of the OMS-2-Supported CuOx Catalysts for Carbon Monoxide, Ethyl Acetate, and Toluene Oxidation
Catalysts 2021, 11(6), 713; https://doi.org/10.3390/catal11060713 - 07 Jun 2021
Cited by 7 | Viewed by 1944
Abstract
Different Cu contents (x wt%) were supported on the cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2) (xCu/OMS-2; x = 1, 5, 15, and 20) via a pre-incorporation method. Physicochemical properties of the OMS-2 and xCu/OMS-2 samples were characterized by [...] Read more.
Different Cu contents (x wt%) were supported on the cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2) (xCu/OMS-2; x = 1, 5, 15, and 20) via a pre-incorporation method. Physicochemical properties of the OMS-2 and xCu/OMS-2 samples were characterized by means of the XRD, FT-IR, SEM, TG/DTG, ICP-OES, XPS, O2-TPD, H2-TPR, and in situ DRIFTS techniques, and their catalytic activities were measured for the oxidation of CO, ethyl acetate, and toluene. The results show that the Cu species were homogeneously dispersed in the tunnel and framework structure of OMS-2. Among all of the samples, 15Cu/OMS-2 sample exhibited the best activities with the T50% of 65, 165, and 240 °C as well as the T90% of 85, 215, and 290 °C for CO, ethyl acetate and toluene oxidation, respectively, which was due to the existence of the Cu species and Mn3+/Mn4+ redox couples, rich oxygen vacancies, good oxygen mobility, low-temperature reducibility, and strong interaction between the Cu species and the OMS-2 support. The reaction mechanisms were also deduced by analyzing the in situ DRIFTS spectra of the 15Cu/OMS-2 sample. The excellent oxygen mobility associated with the electron transfer between Cu species and Mn3+/Mn4+ redox couples might be conducive to the continuous replenishment of active oxygen species and the constantly generated reactant intermediates, thereby increasing the reactant reaction rate. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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14 pages, 4582 KiB  
Article
Selective Catalytic Oxidation of Toluene to Benzaldehyde: Effect of Aging Time and Calcination Temperature Using CuxZnyO Mixed Metal Oxide Nanoparticles
Catalysts 2021, 11(3), 354; https://doi.org/10.3390/catal11030354 - 09 Mar 2021
Cited by 3 | Viewed by 3256
Abstract
Oxidation is an important organic transformation, and several catalysts have been reported for this conversion. In this study, we report the synthesis of mixed metal oxide CuxZnyO, which is prepared by a coprecipitation method by varying the molar ratio [...] Read more.
Oxidation is an important organic transformation, and several catalysts have been reported for this conversion. In this study, we report the synthesis of mixed metal oxide CuxZnyO, which is prepared by a coprecipitation method by varying the molar ratio of Cu and Zn in the catalytic system. The prepared mixed metal oxide CuxZnyO was evaluated for catalytic performance for toluene oxidation. Various parameters of the catalytic evaluation were studied in order to ascertain the optimum condition for the best catalytic performance. The results indicate that aging time, calcination temperature, reaction temperature, and feed rate influence catalytic performance. It was found that the catalyst interfaces apparently enhanced catalytic activity for toluene oxidation. The XRD diffractograms reveal the crystalline nature of the mixed metal oxide formed and also confirm the coexistence of hexagonal and monoclinic crystalline phases. The catalyst prepared by aging for 4 h and calcined at 450 °C was found to be the best for the conversion of toluene to benzaldehyde while the reactor temperature was maintained at 250 °C with toluene fed into the reactor at 0.01 mL/min. The catalyst was active for about 13 h. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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20 pages, 4818 KiB  
Article
Oxidation of 5-Hydroxymethylfurfural on Supported Ag, Au, Pd and Bimetallic Pd-Au Catalysts: Effect of the Support
Catalysts 2021, 11(1), 115; https://doi.org/10.3390/catal11010115 - 14 Jan 2021
Cited by 20 | Viewed by 3302
Abstract
Oxidation of 5-hydroxymethylfurfural (HMF), a major feedstock derived from waste/fresh biomass, into 2,5-furandicarboxylic acid (FDCA) is an important transformation for the production of biodegradable plastics. Herein, we investigated the effect of the support (unmodified and modified titania, commercial alumina, and untreated and treated [...] Read more.
Oxidation of 5-hydroxymethylfurfural (HMF), a major feedstock derived from waste/fresh biomass, into 2,5-furandicarboxylic acid (FDCA) is an important transformation for the production of biodegradable plastics. Herein, we investigated the effect of the support (unmodified and modified titania, commercial alumina, and untreated and treated Sibunit carbon) of mono- and bimetallic catalysts based on noble metals (Ag, Au, Pd) on selective HMF oxidation with molecular oxygen to FDCA under mild and basic reaction conditions. The higher selectivity to FDCA was obtained when metals were supported on Sibunit carbon (Cp). The order of noble metal in terms of catalyst selectivity was: Ag < Au < Pd < PdAu. Finally, FDCA production on the most efficient PdAu NPs catalysts supported on Sibunit depended on the treatment applied to this carbon support in the order: PdAu/Cp < PdAu/Cp-HNO3 < PdAu/Cp-NH4OH. These bimetallic catalysts were characterized by nitrogen adsorption-desorption, inductively coupled plasma atomic emission spectroscopy, high resolution transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Hammet indicator method and X-ray photoelectron spectroscopy. The functionalization of Sibunit surface by HNO3 and NH4OH led to a change in the contribution of the active states of Pd and Au due to promotion effect of N-doping and, as a consequence, to higher FDCA production. HMF oxidation catalyzed by bimetallic catalysts is a structure sensitive reaction. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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12 pages, 8460 KiB  
Article
Reaction Mechanism for Methane-to-Methanol in Cu-SSZ-13: First-Principles Study of the Z2[Cu2O] and Z2[Cu2OH] Motifs
Catalysts 2021, 11(1), 17; https://doi.org/10.3390/catal11010017 - 25 Dec 2020
Cited by 2 | Viewed by 2068
Abstract
As transportation continues to increase world-wide, there is a need for more efficient utilization of fossil fuel. One possibility is direct conversion of the solution gas bi-product CH4 into an energy-rich, easily usable liquid fuel such as CH3OH. However, new [...] Read more.
As transportation continues to increase world-wide, there is a need for more efficient utilization of fossil fuel. One possibility is direct conversion of the solution gas bi-product CH4 into an energy-rich, easily usable liquid fuel such as CH3OH. However, new catalytic materials to facilitate the methane-to-methanol reaction are needed. Using density functional calculations, the partial oxidation of methane is investigated over the small-pore copper-exchanged zeolite SSZ-13. The reaction pathway is identified and the energy landscape elucidated over the proposed motifs Z2[Cu2O] and Z2[Cu2OH]. It is shown that the Z2[Cu2O] motif has an exergonic reaction path, provided water is added as a solvent for the desorption step. However, a micro-kinetic model shows that neither Z2[Cu2O] nor Z2[Cu2OH] has any notable activity under the reaction conditions. These findings highlight the importance of the detailed structure of the active site and that the most stable motif is not necessarily the most active. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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18 pages, 2168 KiB  
Article
Increasing the Efficiency of Optimized V-SBA-15 Catalysts in the Selective Oxidation of Methane to Formaldehyde by Artificial Neural Network Modelling
Catalysts 2020, 10(12), 1411; https://doi.org/10.3390/catal10121411 - 02 Dec 2020
Cited by 10 | Viewed by 2068
Abstract
The present study investigates the possibility of improving the selective oxidation of methane to formaldehyde over V-SBA-15 catalysts in two different ways. In a classical approach of catalyst optimization, the in situ synthesis of V-SBA-15 catalysts was optimized with regard to the applied [...] Read more.
The present study investigates the possibility of improving the selective oxidation of methane to formaldehyde over V-SBA-15 catalysts in two different ways. In a classical approach of catalyst optimization, the in situ synthesis of V-SBA-15 catalysts was optimized with regard to the applied pH value. Among the set of catalysts synthesized, a higher amount of incorporated vanadium, a higher content of polymeric VOx species as well as a less ordered structure of the support material were observed by increasing the pH values from 2.0 to 3.0. An optimum in performance during the selective oxidation of methane to formaldehyde with respect to activity and selectivity was found over V-SBA-15 prepared at a pH value of 2.5. With this knowledge, we have now evaluated the possibilities of reaction control using this catalyst. Specifically, artificial neural network modelling was applied after the collection of 232 training samples for obtaining insight into the influence of different reaction parameters (temperature; gas hourly space velocity (GHSV); and concentration of O2, N2 and H2O) onto methane conversion and selectivity towards formaldehyde. This optimization of reaction conditions resulted in an outstanding high space-time yield of 13.6 kgCH2O∙kgcat∙h−1. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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15 pages, 2369 KiB  
Article
Newly Isolated Alkane Hydroxylase and Lipase Producing Geobacillus and Anoxybacillus Species Involved in Crude Oil Degradation
Catalysts 2020, 10(8), 851; https://doi.org/10.3390/catal10080851 - 01 Aug 2020
Cited by 16 | Viewed by 4634
Abstract
Isolation and studies of novel, crude oil biodegrading thermophilic strains may provide a wider knowledge in understanding their role in petroleum degradation. In this study, the screening of ten new thermophilic strains revealed that all strains were alkane hydroxylase producers and seven of [...] Read more.
Isolation and studies of novel, crude oil biodegrading thermophilic strains may provide a wider knowledge in understanding their role in petroleum degradation. In this study, the screening of ten new thermophilic strains revealed that all strains were alkane hydroxylase producers and seven of them produced lipase concurrently. Three best strains were characterized and identified through 16S rRNA sequence analysis as Geobacillus sp. D4, Geobacillus sp. D7, and Anoxybacillus geothermalis D9 with GenBank accession numbers MK615934.1, MK615935.1, and MK615936.1, respectively. Gas chromatography (GC) analysis showed that all three strains were able to breakdown various compounds in crude oil such as alkanes, toxic poly-aromatic hydrocarbons (PAHs), organosulfur, carboxylic acids, alkene, resins, organosilicon, alcohol, organochlorine, and ester. For the first time, alkane hydroxylase and lipase activity as well as crude oil degradation by A. geothermalis species were reported. Geobacillus sp. D7 is the best alkane degrader followed by A. geothermalis D9 and Geobacillus sp. D4 with 17.3%, 13.1%, and 12.1% biodegradation efficiency (BE%), respectively. The potential of thermophiles isolated can be explored further for bioremediation of sites polluted by petroleum and oil spills. Full article
(This article belongs to the Special Issue Catalytic Oxidation of Hydrocarbons)
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