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Catalysts
Special Issues
Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts
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Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts

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

Deadline for manuscript submissions: closed (31 May 2023) | Viewed by 10411

Special Issue Editors

Dr. Lalit Kumar Golani

E-Mail Website1 Website2
Guest Editor
Department of Chemistry & Biochemistry, Milwaukee Institute for Drug Discovery, University of Wisconsin, Milwaukee, WI 53211, USA
Interests: organic chemistry; total synthesis; natural products; stereoselective synthesis and drug design
Dr. Fan Zhang

E-Mail Website
Guest Editor
National Institute of Clean-and-Low-Carbon Energy, Beijing 102211, China
Interests: coal chemical industry; catalysts for methanol synthesis

Special Issue Information

Dear Colleagues,

Catalytic hydrogenation and dehydrogenation of functional groups in organic molecules are useful, versatile, and environmentally friendly reaction routes available for organic synthesis. This important area of catalytic chemistry has vital scientific significance and broad application prospects in energy storage, fine chemicals, production of polymers, production of edible and non-edible oils, and pharmaceuticals synthesis. About 10–20% of chemical reactions used to produce fine chemicals and pharmaceutical products are hydrogenations. Dehydrogenation reactions find wide application in the production of hydrogen, alkenes (especially, light olefins, that is, ethene and propene), polymers, and oxygenates. Reversible dehydrogenation reactions (hydrogen release process) and hydrogenation reactions (hydrogen storage process) are used as hydrogen storage systems through various organic hydrogen carriers.  

This Special Issue will cover recent developments in catalysts for hydrogenation and dehydrogenation reactions.

Dr. Lalit Kumar Golani
Dr. Fan Zhang
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 submissions that pass pre-check are 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 2700 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.

Keywords

  • Catalytic hydrogenation
  • Catalytic dehydrogenation
  • Energy storage
  • Hydrogen production
  • Pharmaceuticals synthesis
  • Light olefins

Published Papers (6 papers)

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Research

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15 pages, 3281 KiB  
Article
CO2 Hydrogenation to Methanol on CuO-ZnO/SiO2 and CuO-ZnO/CeO2-SiO2 Catalysts Synthesized with β-Cyclodextrin Template
by Andrey E. Vertepov, Anna A. Fedorova, Alexander M. Batkin, Alexander V. Knotko, Konstantin I. Maslakov, Vladimir D. Doljenko, Alexander V. Vasiliev, Gennadiy I. Kapustin, Tatyana B. Shatalova, Nadezhda M. Sorokina, Leonid M. Kustov, Igor V. Morozov and Alexander L. Kustov
Catalysts 2023, 13(9), 1231; https://doi.org/10.3390/catal13091231 - 23 Aug 2023
Cited by 1 | Viewed by 1000
Abstract
A series of mixed copper (II)—zinc oxide catalysts supported on unmodified and ceria-modified silica supports were synthesized using β-cyclodextrin as a template. The novelty of this work lies in the use of cyclosextrins for the template synthesis of catalyst supports. The obtained samples [...] Read more.
A series of mixed copper (II)—zinc oxide catalysts supported on unmodified and ceria-modified silica supports were synthesized using β-cyclodextrin as a template. The novelty of this work lies in the use of cyclosextrins for the template synthesis of catalyst supports. The obtained samples were analyzed by XRD, SEM-EDX, low-temperature nitrogen physisorption, XPS, and EPR. The magnetic properties of the catalysts were also measured. The thermal decomposition of precursors was analyzed by TGA combined with mass-spectrometric analysis of the evolved gases. The effects of the support pore size, the nature of the active phase and its loading, as well as the sequence of component deposition on the catalyst performance in the CO2 conversion to methanol were studied. The catalysts with cerium added at the gelation stage demonstrated the best performance. The selectivity of these samples reaches values of more than 90% over a fairly ide temperature range, with the productivity reaching 480 g/kg cat·h at 300 °C. Full article
(This article belongs to the Special Issue Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts)
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20 pages, 4429 KiB  
Article
The Effect of a Nitrogen-Based Ionic Liquid as a Coating over 1Pd9Ag/Al2O3 for the Selective Hydrogenation of 1,7-Octadiene vs 1-Octene
by Revana Chanerika, Mzamo L. Shozi, Mirko Prato and Holger B. Friedrich
Catalysts 2023, 13(4), 746; https://doi.org/10.3390/catal13040746 - 13 Apr 2023
Cited by 1 | Viewed by 1193
Abstract
The effect of tetrabutylammonium nitrate ([N4444][NO3]) was studied as a surface coating over 1Pd9Ag/Al2O3 and applied in the selective hydrogenation of 1,7-octadiene in a mixture with 1-octene. Weight loadings up to a surface of three monolayers [...] Read more.
The effect of tetrabutylammonium nitrate ([N4444][NO3]) was studied as a surface coating over 1Pd9Ag/Al2O3 and applied in the selective hydrogenation of 1,7-octadiene in a mixture with 1-octene. Weight loadings up to a surface of three monolayers (MLs) were investigated and a further comparison coating with 1-ethylimidazole ([EIM]) was carried out to assess anionic effects in the Solid Catalysts with an Ionic Liquid Layer (SCILLs). Catalysts were characterised by H2-chemisorption, TGA-DSC, BET measurements, XPS, and HR-TEM. Catalytic studies showed that the uncoated and EIM-coated (10 wt%) catalysts gave nearly a 100% conversion of 1,7-octadiene and 1-octene with a selectivity mainly towards octane. Coating with [N4444][NO3] at 1 ML significantly decreased the 1-octene conversion by almost 50%, as well as the selectivity to octane (38%) at close to a 100% diene conversion. However, no net gain in 1-octene in the output stream was noted. At 2 ML IL/EIM coverage, a further decline in 1-octene conversion and octane selectivity was found at a diene conversion of 75%. The selectivity to 1-octene steadily increased from over the bare catalyst (52%) to the EIM-coated (62%) catalyst and SCILL (75%). At 3 ML IL coverage, the diene conversion (35%) was significantly reduced due to mass transfer limitations of hydrogen through the thick IL layer. Characterisation of the used catalysts by TG and BET analyses confirmed a leaching of up to 14% of the ionic liquid in the SCILLs coated at 1 ML and 2 ML, with an increase in surface area noted. Furthermore, smaller particle sizes of the used catalysts showed that the metal–support interaction was re-established. These results confirm a mild ligand coordination between the nitrogen in the IL anion and Pd and Ag where the ionic liquid remained physisorbed over the surface of the catalyst. In addition, component miscibility tests revealed partial solubility of the diene in the ionic liquid, indicating the presence of solvent effects also. Full article
(This article belongs to the Special Issue Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts)
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20 pages, 3983 KiB  
Article
Analysis of the Effectiveness Factor in a Fixed-Bed Tubular Reactor System: Catalytic Dehydrogenation of Cyclohexanol
by Luis Américo Carrasco-Venegas, José Vulfrano González-Fernández, Luz Genara Castañeda-Pérez, Juan Taumaturgo Medina-Collana, Guido Palomino-Hernández, Daril Giovanni Martínez-Hilario and Salvador Apolinar Trujillo-Pérez
Catalysts 2023, 13(3), 585; https://doi.org/10.3390/catal13030585 - 14 Mar 2023
Cited by 3 | Viewed by 1764
Abstract
The modeling and simulation of the catalytic dehydrogenation process of cyclohexanol in a fixed-bed catalytic reactor is presented, leading to finding the relationship between the effectiveness factor, the Thiele modulus, and the Weisz–Prater modulus of the catalyst particles with respect to their axial [...] Read more.
The modeling and simulation of the catalytic dehydrogenation process of cyclohexanol in a fixed-bed catalytic reactor is presented, leading to finding the relationship between the effectiveness factor, the Thiele modulus, and the Weisz–Prater modulus of the catalyst particles with respect to their axial and radial position, for which the external conditions of concentration and temperature around each particle were previously obtained by applying the material and energy balances in the catalyst bed considering a two-dimensional pseudo-homogeneous model with radial diffusion. Subsequently, the material balances are established in terms of the molar flux density and conversion, the energy balance in terms of the heat flux density, Fick’s law, Fourier’s law, and the differential form of the effectiveness factor non-isothermal for each particle chosen based on the proposed meshing. The Thiele modulus calculated for most of the points is between 0.8 and 0.25, with a tendency towards the lower limit, and the theoretical values established as the limit for the Thiele modulus fluctuate between 0.4<Th<4. Therefore, the effectiveness factor analyzed is between 1 and 1/Th; this indicates that both the reaction speed as well as the diffusion speed within the particle have an influence on the intraparticle process, which is confirmed by the calculation of the Weisz–Prater modulus whose values are not <<1 nor >>1. The results obtained are subjected to a statistical test leading to analyzing whether there are significant differences both in the Thiele modulus, as well as in the effectiveness factor with respect to the radius and length of the reactor. It has been determined that there are no significant differences between the effectiveness factor with respect to the radius of the reactor; however, according to the analysis of variance, there are significant differences in the effectiveness factor with respect to length and, likewise, there are significant differences in the Thiele modulus and the Weisz–Prater modulus with respect to radius and length. Full article
(This article belongs to the Special Issue Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts)
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18 pages, 10256 KiB  
Article
Catalytic Hydrogenation of Nitrocyclohexane with CuCo/SiO2 Catalysts in Gas and Liquid Flow Reactors
by Emil Kowalewski, Krzysztof Matus, Arkadiusz Gajek and Anna Śrębowata
Catalysts 2022, 12(9), 1062; https://doi.org/10.3390/catal12091062 - 17 Sep 2022
Cited by 3 | Viewed by 1594
Abstract
Catalytic hydrogenation of nitrocyclohexane proved to be an attractive alternative source of various chemical compounds: cyclohexanone oxime, cyclohexanone, cyclohexanol, cyclohexylamine and dicyclohexylamine. A growing interest in this reaction has been observed in the last few years. Herein, we present the catalytic performance of [...] Read more.
Catalytic hydrogenation of nitrocyclohexane proved to be an attractive alternative source of various chemical compounds: cyclohexanone oxime, cyclohexanone, cyclohexanol, cyclohexylamine and dicyclohexylamine. A growing interest in this reaction has been observed in the last few years. Herein, we present the catalytic performance of Cu/SiO2, Co/SiO2 and CuCo/SiO2 in gas and liquid flow nitrocyclohexane hydrogenation. The analysis of synthesized catalysts morphology (BET, TPR, XRD, TEM) in terms of their catalytic behavior allows us to draw general conclusions and determine the optimal conditions for the production of desired products. Application of the monometallic copper leads to the formation of cyclohexanone as the main product, but with low activity. On the other hand, Co/SiO2 shows high activity but gives cyclohexylamine. Bimetallic system CuCo(3:1)/SiO2 allows for the efficient production of 100% cyclohexanone at 5 bar and 75 °C. Full article
(This article belongs to the Special Issue Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts)
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13 pages, 2611 KiB  
Article
Preparation of a Novel NiAlO Composite Oxide Catalyst for the Dehydrogenation of Methylcyclohexane
by Dongliang Wang, Qian Lei, Hongwei Li, Guixian Li and Yu Zhao
Catalysts 2022, 12(9), 958; https://doi.org/10.3390/catal12090958 - 29 Aug 2022
Cited by 1 | Viewed by 1574
Abstract
A series of NiAlO composite oxide catalysts with high surface areas and high Ni dispersion were prepared through an improved co-precipitation method. The new preparation method effectively improved the specific surface area and pore volume of the catalyst, promoted the dispersion of nickel [...] Read more.
A series of NiAlO composite oxide catalysts with high surface areas and high Ni dispersion were prepared through an improved co-precipitation method. The new preparation method effectively improved the specific surface area and pore volume of the catalyst, promoted the dispersion of nickel species, alleviated the agglomeration of the catalyst, and improved the stability of the catalyst by strengthening the interaction between Ni and Al. The typical catalyst Ni20Al had a specific surface area of 359 m2/g and a NiAl2O4 phase. In the dehydrogenation of methylcyclohexane over the Ni20Al catalyst, the conversion of methylcyclohexane could reach 77.4%, with toluene selectivity of 85.6%, and a hydrogen release rate of 63.94 mmol g−1 h−1, and did not show any significant inactivation during the stability test over 29 h under the reaction conditions of reaction temperature 450 °C and LHSV = 4 mL g−1 h−1. However, the conversion of methylcyclohexane with the IM-NiAl catalyst prepared through the traditional impregnation method was only 50.75%, with toluene selectivity of 70.5%, and with a hydrogen release rate of 35.84 mmol g−1 h−1, and the lifetime of the catalyst was only 15 h. Full article
(This article belongs to the Special Issue Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts)
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Review

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22 pages, 5652 KiB  
Review
In Situ Surface Reconstruction of Catalysts for Enhanced Hydrogen Evolution
by Yingbo Zhang, Junan Pan, Gu Gong, Renxuan Song, Ye Yuan, Mengzhu Li, Weifeng Hu, Pengcheng Fan, Lexing Yuan and Longlu Wang
Catalysts 2023, 13(1), 120; https://doi.org/10.3390/catal13010120 - 05 Jan 2023
Cited by 3 | Viewed by 1996
Abstract
The in situ surface reconstitution of a catalyst for hydrogen evolution refers to its structure evolution induced by strong interactions with reaction intermediates during the hydrogen evolution reaction (HER), which eventually leads to the self-optimization of active sites. In consideration of the superior [...] Read more.
The in situ surface reconstitution of a catalyst for hydrogen evolution refers to its structure evolution induced by strong interactions with reaction intermediates during the hydrogen evolution reaction (HER), which eventually leads to the self-optimization of active sites. In consideration of the superior performance that can be achieved by in situ surface reconstitution, more and more attention has been paid to the relationship between active site structure evolution and the self-optimization of HER activity. More and more in situ and/or operando techniques have been explored to track the dynamic structural evolution of HER catalysts in order to clarify the underlying mechanism. This review summarizes recent advances in various types of reconstruction such as the reconfiguration of crystallinity, morphological evolution, chemical composition evolution, phase transition refactoring, surface defects, and interface refactoring in the HER process. Finally, different perspectives and outlooks are offered to guide future investigations. This review is expected to provide some new clues for a deeper understanding of in situ surface reconfiguration in hydrogen evolution reactions and the targeted design of catalysts with desirable structures. Full article
(This article belongs to the Special Issue Recent Progress in Development of Hydrogenation and Dehydrogenation Catalysts)
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