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New Developments in Heterogeneous Partial and Total Oxidation Catalysis

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

Deadline for manuscript submissions: closed (16 September 2018) | Viewed by 70051

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Prof. Dr. Jacques Charles Védrine

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Sorbonne université, Université Pierre et Marie Curie, Paris, France
Interests: Partial oxidation reactions catalysis, zeolites and porous materials, acid-base catalysis, physical techniques of characterisation of solid materials and of reaction intermediates
Special Issues, Collections and Topics in MDPI journals

Dr. Sabine Valange

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Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), UMR CNRS 7285, Université de Poitiers, Ecole Nationale Supérieure d'Ingénieurs de Poitiers, 1 Rue Marcel Doré, TSA 41105, CEDEX 9, 86073 Poitiers, France
Interests: catalyst synthesis; porous materials; nanostructured oxides; heterogeneous catalysis; selective oxidation; total oxidation; biomass valorization; ball-milling; ultrasound; sonochemistry; sonocatalysis; sustainable chemistry
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Oxana Kholdeeva

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Boreskov Institute of Catalysis SB RAS Pr. akademika Lavrentieva 5, 630090 Novosibirsk, Russia
Interests: liquid-phase selective oxidation of organic compounds; catalysis of environmentally benign processes; green chemistry; single-site heterogeneous catalysts; supported catalysts; polyoxometalates; design of catalytic centres; structure/activity/selectivity relationships in catalysis; mechanisms of catalytic oxidations

Dr. James F. Brazdil

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William A. Brookshire Department of Chemical and Biomolecular Engineering, University of Houston, TX 77204, USA
Interests: Industrial catalysis, selective oxidation and ammoxidation catalysis, catalyst characterization, solid state chemistry, catalyst manufacture, catalysis for upgrading bio-derived feedstocks

Special Issue Information

Dear colleagues,

This Special Issue aims at considering the state-of-the-art of catalysis by selective partial and total oxidation reactions on metal oxides and to emphasise on the recent developments in catalytic reactions, in reactors designs (chemical engineering), in the preparation and activation procedures of solid materials. Academic and industrial views and case studies will be given for the understanding of the catalyst action and reaction mechanisms and for the future extent and trends of the domain, with special emphasis on the use of biomass and renewable raw chemicals.

Prof. Dr. Jacques Charles Védrine
Assoc. Prof. Dr. Sabine Valange
Prof. Dr. Oxana Kholdeeva
Dr. James F. Brazdil
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

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Keywords

heterogeneous catalysis
partial oxidation reactions
academic and industrial examples and views
trends for the future

Published Papers (11 papers)

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Research

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31 pages, 3390 KiB

Open AccessArticle

Constructing A Rational Kinetic Model of the Selective Propane Oxidation Over A Mixed Metal Oxide Catalyst

by Christoph Sprung, Gregory S. Yablonsky, Robert Schlögl and Annette Trunschke

Catalysts 2018, 8(8), 330; https://doi.org/10.3390/catal8080330 - 13 Aug 2018

Cited by 14 | Viewed by 4434

Abstract

This research presents a kinetic investigation of the selective oxidation of propane to acrylic acid over a MoVTeNb oxide (M1 phase) catalyst. The paper contains both an overview of the related literature, and original results with a focus on kinetic aspects. Two types of kinetic experiments were performed in a plug flow reactor, observing (i) steady-state conditions (partial pressure variations) and (ii) the catalyst evolution as a function of time-on-stream. For this, the catalyst was treated in reducing atmosphere, before re-oxidising it. These observations in long term behaviour were used to distinguish different catalytic routes, namely for the formation of propene, acetic acid, acrylic acid, carbon monoxide and carbon dioxide. A partial carbon balance was introduced, which is a ‘kinetic fingerprint’, that distinguishes one type of active site from another. Furthermore, an ‘active site’ was found to consist of one or more ‘active centres’. A rational mechanism was developed based on the theory of graphs and includes two time scales belonging to (i) the catalytic cycle and (ii) the catalyst evolution. Several different types of active sites exist, at least as many, as kinetically independent product molecules are formed over a catalyst surface. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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10 pages, 1234 KiB

Open AccessFeature PaperArticle

The Low Temperature Solvent-Free Aerobic Oxidation of Cyclohexene to Cyclohexane Diol over Highly Active Au/Graphite and Au/Graphene Catalysts

by Owen Rogers, Samuel Pattisson, Joseph Macginley, Rebecca V. Engel, Keith Whiston, Stuart H. Taylor and Graham J. Hutchings

Catalysts 2018, 8(8), 311; https://doi.org/10.3390/catal8080311 - 31 Jul 2018

Cited by 14 | Viewed by 4755

Abstract

The selectivity and activity of gold-catalysts supported on graphite and graphene have been compared in the oxidation of cyclohexene. These catalysts were prepared via impregnation and sol immobilisation methods, and tested using solventless and radical initiator-free reaction conditions. The selectivity of these catalysts has been directed towards cyclohexene epoxide using WO₃ as a co-catalyst and further to cyclohexane diol by the addition of water, achieving a maximum selectivity of 17% to the diol. The sol immobilisation catalysts were more reproducible and far more active, however, selectivity towards the diol was lower than for the impregnation catalyst. The results suggest that formation of cyclohexane diol through solventless oxidation of cyclohexene is limited by a number of factors, such as the formation of an allylic hydroperoxyl species as well as the amount of in situ generated water. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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18 pages, 2954 KiB

Open AccessArticle

Vanadium Supported on Alumina and/or Zirconia Catalysts for the Selective Transformation of Ethane and Methanol

by Souhila Benomar, Amada Massó, Benjamín Solsona, Rachid Issaadi and Jose M. López Nieto

Catalysts 2018, 8(4), 126; https://doi.org/10.3390/catal8040126 - 22 Mar 2018

Cited by 12 | Viewed by 5678

Abstract

Vanadium supported on pure (Al₂O₃, ZrO₂) or mixed zirconia-alumina (with Al/(Al + Zr) ratio of 0.75 or 0.25) catalysts have been prepared by wet impregnation, using homemade prepared supports. The catalysts have been characterized and tested in the oxidative dehydrogenation (ODH) of ethane and in the methanol aerobic transformation. The catalytic performance strongly depends on the nature of the metal oxide support. Thus, activity decreases in the order: VOx/ZrO₂ > VOx/(Al,Zr-oxides) > VOx/Al₂O₃. On the other hand, at low and medium ethane conversions, the selectivity to ethylene presents an opposite trend: VOx/Al₂O₃ > VOx/(Al,Zr-oxides) > VOx/ZrO₂. The different selectivity to ethylene at high conversion is due to the lower/higher initial ethylene formation and to the extent of the ethylene decomposition. Interestingly, VOx/(Al,Zr-oxides) with low Zr-loading present the lowest ethylene decomposition. The catalytic results obtained mainly depend on the nature of the supports whereas the role of the dispersion of vanadium species is unclear. In methanol oxidation, the catalysts tested present similar catalytic activity regardless of the support (Al₂O₃, ZrO₂ or mixed Al₂O₃-ZrO₂) but strong differences in the selectivity to the reaction products. Thus, dimethyl ether was mainly observed on alumina-supported vanadium oxide catalysts (which is associated to the presence of acidic sites on the surface of the catalyst, as determined by TPD-NH₃). Formaldehyde was the main reaction product on catalysts supported on Zr-containing oxides (which can be related to a low presence of acid sites). In this article, the importance of the presence of acid sites in ethane ODH, which can be estimated using the methanol transformation reaction, is also discussed. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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20 pages, 4458 KiB

Open AccessFeature PaperArticle

Tungsten-Based Mesoporous Silicates W-MMM-E as Heterogeneous Catalysts for Liquid-Phase Oxidations with Aqueous H₂O₂

by Nataliya Maksimchuk, Irina Ivanchikova, Olga Zalomaeva, Yurii Chesalov, Alexandr Shmakov, Vladimir Zaikovskii and Oxana Kholdeeva

Catalysts 2018, 8(3), 95; https://doi.org/10.3390/catal8030095 - 27 Feb 2018

Cited by 10 | Viewed by 3941

Abstract

Mesoporous tungsten-silicates, W-MMM-E, have been prepared following evaporation-induced self-assembly methodology and characterized by elemental analysis, XRD, N₂ adsorption, STEM-HAADF (high angle annular dark field in scanning-TEM mode), DRS UV-vis, and Raman techniques. DRS UV-vis showed the presence of two types of tungsten oxo-species in W-MMM-E samples: isolated tetrahedrally and oligomeric octahedrally coordinated ones, with the ratio depending on the content of tungsten in the catalyst. Materials with lower W loading have a higher contribution from isolated species, regardless of the preparation method. W-MMM-E catalyzes selectively oxidize of a range of alkenes and organic sulfides, including bulky terpene or thianthrene molecules, using green aqueous H₂O₂. The selectivity of corresponding epoxides reached 85–99% in up to 80% alkene conversions, while sulfoxides formed with 84–90% selectivity in almost complete sulfide conversions and a 90–100% H₂O₂ utilization efficiency. The true heterogeneity of catalysis over W-MMM-E was proved by hot filtration tests. Leaching of inactive W species depended on the reaction conditions and initial W loading in the catalyst. After optimization of the catalyst system, it did not exceed 20 ppm and 3 ppm for epoxidation and sulfoxidation reactions, respectively. Elaborated catalysts could be easily retrieved by filtration and reused several times with maintenance of the catalytic behavior. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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10 pages, 3223 KiB

Open AccessArticle

Aerobic Oxidation of Benzyl Alcohol on a Strontium-Based Gold Material: Remarkable Intrinsic Basicity and Reusable Catalyst

by Karla Patrícia R. Castro, Marco Aurélio S. Garcia, Wiury C. de Abreu, Samuel Anderson A. de Sousa, Carla Verônica R. de Moura, Jean Cláudio S. Costa and Edmilson M. de Moura

Catalysts 2018, 8(2), 83; https://doi.org/10.3390/catal8020083 - 15 Feb 2018

Cited by 17 | Viewed by 4101

Abstract

The development of stable and active gold catalysts has arisen as a significant strategy for oxidation of alcohols. Nano-size PVA-stabilized gold nanoparticles immobilized on Sr(OH)₂ by colloidal deposition presented high catalytic activity for benzyl alcohol oxidation. In 2.5 h, 2 bar of O₂ and without extra-base addition, the calcined support reached 54.6% (100 °C) and 67.4% (140 °C) of conversion, presenting the remarkable and unexplored intrinsic basicity that strontium-based materials retain. With sub-stoichiometric K₂CO₃ adding, under the same catalytic conditions, the catalyst conducted the reaction with similar activity, but with excellent reusability in the process, without any gold leaching. We investigated the influence that the support synthesis method and the solvent used for the NPs stabilization have on the oxidation activity. The produced materials were fully characterized by XPS, Rietveld refinement, and TEM. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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2932 KiB

Open AccessArticle

Fe-Doped TiO₂ Supported on HY Zeolite for Solar Photocatalytic Treatment of Dye Pollutants

by Ghania Foura, Nawel Chouchou, Ahcène Soualah, Kahina Kouachi, Matteo Guidotti and Didier Robert

Catalysts 2017, 7(11), 344; https://doi.org/10.3390/catal7110344 - 14 Nov 2017

Cited by 29 | Viewed by 7706

Abstract

Zeolite-supported TiO₂ and Fe-doped TiO₂/zeolite photocatalysts were synthesized, aiming at improving the adsorption properties of the microporous support towards polluting dyes and the photocatalytic performance of TiO₂ in the treatment of the adsorbed organics. The TiO₂/HY zeolite catalyst exhibited the best performance in the photocatalytic degradation of methylene blue, MB, over 10 wt% TiO₂/HY under UV light at 254 nm. The addition of Fe species in the synthesis mixture led to Fe-TiO₂/HY catalyst. The combination of adequate zeolite, good titanium dioxide dispersion, and Fe doping led to a remarkable performance in the degradation of the model dye. Over a 10 wt% Fe-doped TiO₂/HY catalyst a total removal of MB (>98%) was achieved after 60 min under very mild conditions and simple visible light irradiation. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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Review

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14 pages, 1167 KiB

Open AccessReview

V-Containing Mixed Oxide Catalysts for Reduction–Oxidation-Based Reactions with Environmental Applications: A Short Review

by M. Olga Guerrero-Pérez

Catalysts 2018, 8(11), 564; https://doi.org/10.3390/catal8110564 - 20 Nov 2018

Cited by 20 | Viewed by 4935

Abstract

V-containing mixed oxide catalytic materials are well known as active for partial oxidation reactions. Oxidation reactions are used in industrial chemistry and for the abatement of pollutants. An analysis of the literature in this field during the past few years shows a clear increase in the use of vanadium-based materials as catalysts for environmental applications. The present contribution makes a brief revision of the main applications of vanadium containing mixed oxides in environmental catalysis, analyzing the properties that present the catalysts with a better behavior that, in most cases, is related with the stabilization of reduced vanadium species (as V⁴⁺/V³⁺) during reaction. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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21 pages, 3491 KiB

Open AccessReview

General and Prospective Views on Oxidation Reactions in Heterogeneous Catalysis

by Sabine Valange and Jacques C. Védrine

Catalysts 2018, 8(10), 483; https://doi.org/10.3390/catal8100483 - 22 Oct 2018

Cited by 43 | Viewed by 6879

Abstract

In this review paper, we have assembled the main characteristics of partial oxidation reactions (oxidative dehydrogenation and selective oxidation to olefins or oxygenates, as aldehydes and carboxylic acids and nitriles), as well as total oxidation, particularly for depollution, environmental issues and wastewater treatments. Both gas–solid and liquid–solid media have been considered with recent and representative examples within these fields. We have also discussed about their potential and prospective industrial applications. Particular attention has been brought to new raw materials stemming from biomass, as well as to liquid–solid catalysts cases. This review paper also summarizes the progresses made in the use of unconventional activation methods for performing oxidation reactions, highlighting the synergy of these technologies with heterogeneous catalysis. Focus has been centered on both usual catalysts activation methods and less usual ones, such as the use of ultrasounds, microwaves, grinding (mechanochemistry) and photo-activated processes, as well as their combined use. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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54 pages, 9537 KiB

Open AccessReview

Ag-Based Catalysts in Heterogeneous Selective Oxidation of Alcohols: A Review

by Viktoriia V. Torbina, Andrei A. Vodyankin, Sergey Ten, Grigory V. Mamontov, Mikhail A. Salaev, Vladimir I. Sobolev and Olga V. Vodyankina

Catalysts 2018, 8(10), 447; https://doi.org/10.3390/catal8100447 - 11 Oct 2018

Cited by 62 | Viewed by 11272

Abstract

Alcohols (bioalcohols) is a class of chemicals that are used as a feedstock for the manufacturing of a large number of valuable intermediates in industrially important processes. Currently, sustainable technologies for selective conversion of alcohols utilize “green” oxidants, mainly, ambient air or oxygen. Due to the high affinity of oxygen towards silver, the latter serves as an active component of supported heterogeneous catalysts. In this review, we consider Ag-based catalysts that participate in gas- or liquid-phase oxidation of alcohols. Oxidation of methanol, ethanol, ethylene glycol, propylene glycol, glycerol, benzyl and allyl alcohols is mostly considered. A particular attention is paid to selective photooxidation of alcohols over Ag-based catalysts. We discuss the catalyst composition in terms of (1) the state of the active component, (2) the nature of the substrate, (3) support nature, and (4) the strength of the metal–support interactions. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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19 pages, 2224 KiB

Open AccessReview

Designing Multifunctionality into Single Phase and Multiphase Metal-Oxide-Selective Propylene Ammoxidation Catalysts

by James F. Brazdil

Catalysts 2018, 8(3), 103; https://doi.org/10.3390/catal8030103 - 02 Mar 2018

Cited by 10 | Viewed by 4976

Abstract

Multifunctionality is the hallmark of most modern commercial heterogeneous catalyst systems in use today, including those used for the selective ammoxidation of propylene to acrylonitrile. It is the quintessential principle underlying commercial catalyst design efforts since petrochemical process development is invariably driven by the need to reduce manufacturing costs. This is in large part achieved through new and improved catalysts that increase selectivity and productivity. In addition, the future feedstocks for chemical processes will be invariably more refractory than those currently in use (e.g., replacing alkenes with alkanes or using CO₂), thus requiring a disparate combination of chemical functions in order to effect multiple chemical transformations with the fewest separate process steps. This review summarizes the key chemical phenomena behind achieving the successful integration of multiple functions into a mixed-metal-oxide-selective ammoxidation catalyst. An experiential and functional catalyst design model is presented that consists of one or both of the following components: (1) a mixed-metal-oxide–solid solution where the individual metal components serve separate and necessary functions in the reaction mechanism through their atomic level interaction in the context of a single crystallographic structure; (2) the required elemental components and their catalytic function existing in separate phases, where these phases are able to interact for the purposes of electron and lattice oxygen transfer through the formation of a structurally coherent interface (i.e., epitaxy) between the separate crystal structures. Examples are provided from the literature and explained in the context of this catalyst design model. The extension of the model concepts to the design of heterogeneous catalysts in general is also discussed. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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Other

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17 pages, 1448 KiB

Open AccessPerspective

Oxidative Cleavage of Fatty Acid Derivatives for Monomer Synthesis

by Ana Soutelo-Maria, Jean-Luc Dubois, Jean-Luc Couturier and Giancarlo Cravotto

Catalysts 2018, 8(10), 464; https://doi.org/10.3390/catal8100464 - 17 Oct 2018

Cited by 28 | Viewed by 10163

Abstract

Oxidative cleavage of fatty acids and fatty acid derivatives is a practical way to obtain bifunctional molecules that can be used in polycondensation reactions. Diacids, hydroxyacids, and amino acids can then be used to produce polyesters or polyamides and also a large range of other products, such as lubricants and plasticizers. Ozonolysis has long been the sole industrial process for oxidative cleavage, but recently, routes using hydrogen peroxide as a clean oxidant have regained interest. Hydrogen peroxide is easier to use, but the kinetics of the catalyzed reactions are still slow. Although several catalytic systems have been described in the literature, tungsten-based catalysts are still the preferred choices. Different catalysts can trigger different mechanisms, such as a radical mechanism instead of a catalytic reaction. In addition, some side products and co-products often disregarded in the literature, such as shorted cleavage products, indicate the presence of side reactions that affect the quality of the final products. The oxidative cleavages in continuous and batch processes have significant differences, which are discussed with an illustration of our understanding of the process used by Matrica S.p.A. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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