Mechanism and Kinetics of Complex Reactions— 2020 Selected Papers from Reactions’ Editorial Board Members

A special issue of Reactions (ISSN 2624-781X).

Deadline for manuscript submissions: closed (31 December 2020) | Viewed by 12985

Special Issue Editors


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Special Issue Information

Dear Colleagues,

We are pleased to announce a new Special Issue which is compiling a collection of papers submitted exclusively by its Editorial Board Members (EBMs) covering a specific area of complex reactions. The intention is to address mechanisms of complex chemical reactions with the emphasis on catalytic ones, illustrate how a combination of modern experimental and theoretical methods is bringing forward knowledge about reaction mechanisms and finally link such mechanistic understanding to reaction engineering aspects of complex reactions.

Prof. Dr. Dmitry Yu. Murzin
Dr. Irina L. Simakova
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. Reactions is an international peer-reviewed open access quarterly 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.

Keywords

  • Complex Reactions
  • Mechanisms and Kinetics
  • Reaction Network Analysis
  • One-pot, Tandem, Domino Reactions
  • Heterogeneous Catalysis
  • Homogeneous catalysis
  • Organometallic chemistry
  • Kinetic modelling
  • Chemical Reaction Engineering
  • Catalytic Reaction Engineering

Published Papers (3 papers)

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Research

18 pages, 3083 KiB  
Article
Heterogeneously Catalyzed γ-Valerolactone Hydrogenation into 1,4-Pentanediol in Milder Reaction Conditions
by Irina Simakova, Yulia Demidova, Mikhail Simonov, Sergey Prikhod’ko, Prashant Niphadkar, Vijay Bokade, Paresh Dhepe and Dmitry Yu. Murzin
Reactions 2020, 1(2), 54-71; https://doi.org/10.3390/reactions1020006 - 16 Oct 2020
Cited by 13 | Viewed by 3402
Abstract
Hydrogenation of γ-valerolactone (GVL) in polar solvents (n-butanol, 1,4-dioxane) to 1,4-pentanediol (PDO) and 2-methyltetrahydrofuran (MTHF) was performed at 363–443 K in a fixed bed reactor under overall H2 pressure of 0.7–1.3 MPa. Preliminary screening in a batch reactior was performed [...] Read more.
Hydrogenation of γ-valerolactone (GVL) in polar solvents (n-butanol, 1,4-dioxane) to 1,4-pentanediol (PDO) and 2-methyltetrahydrofuran (MTHF) was performed at 363–443 K in a fixed bed reactor under overall H2 pressure of 0.7–1.3 MPa. Preliminary screening in a batch reactior was performed with a series of Ru, Ir, Pt, Co, and Cu catalysts, earlier efficiently applied for levulinic acid hydrogenation to GVL. The fresh catalysts were analyzed by transmission electron microscopy (TEM), X-ray fluorescent analysis (XRF), temperature programmed reduction by H2 (H2-TPR), and N2 physisorption. Cu/SiO2 prepared by reduction of copper hydroxosilicate with chrysocolla mineral structure provided better selectivity of 67% towards PDO at 32% GVL conversion in a continuous flow reactor. This catalyst was applied to study the effect of temperature, hydrogen pressure, and contact time. The main reaction products were PDO, MTHF, and traces of pentanol, while no valeric acid was observed. Activity and selectivity to PDO over Cu/SiO2 did not change over 9 h, indicating a fair resistance of copper to leaching. Full article
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10 pages, 1389 KiB  
Article
Requiem for the Rate-Determining Step in Complex Heterogeneous Catalytic Reactions?
by Dmitry Yu. Murzin
Reactions 2020, 1(1), 37-46; https://doi.org/10.3390/reactions1010004 - 10 Sep 2020
Cited by 5 | Viewed by 4604
Abstract
The concept of the rate determining step, i.e., the step having the strongest influence on the reaction rate or even being the only one present in the rate equation, is often used in heterogeneous catalytic reactions. The utilization of this concept mainly stems [...] Read more.
The concept of the rate determining step, i.e., the step having the strongest influence on the reaction rate or even being the only one present in the rate equation, is often used in heterogeneous catalytic reactions. The utilization of this concept mainly stems from a need to reduce complexity in deriving explicit rate equations or searching for a better catalyst based on the theoretical insight. When the aim is to derive a rate equation with eventual kinetic modelling for single-route mechanisms with linear sequences, the analytical rate expressions can be obtained based on the theory of complex reactions. For such mechanisms, a single rate limiting step might not be present at all and the common practice of introducing such steps is due mainly to the convenience of using simpler expressions. For mechanisms with a combination of linear and nonlinear steps or those just comprising non-linear steps, the reaction rates are influenced by several steps depending on reaction conditions, thus a reduction in complexity to a single rate limiting step can lead to misinterpretations. More widespread utilization of a microkinetic approach when the reaction rate constants can be computed with reasonable accuracy based on the theoretical insight, and availability of software for kinetic modelling, when a system of differential equations for reactants and products will be solved together with differential equations for catalytic species and the algebraic conservation equation for the latter, will eventually make the concept of the rate limiting step obsolete. Full article
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21 pages, 3018 KiB  
Article
An Iron(III) Complex with Pincer Ligand—Catalytic Water Oxidation through Controllable Ligand Exchange
by Sahir M. Al-Zuraiji, Dávid Lukács, Miklós Németh, Krisztina Frey, Tímea Benkó, Levente Illés and József S. Pap
Reactions 2020, 1(1), 16-36; https://doi.org/10.3390/reactions1010003 - 13 Aug 2020
Cited by 6 | Viewed by 4114
Abstract
Pincer ligands occupy three coplanar sites at metal centers and often support both stability and reactivity. The five-coordinate [FeIIICl2(tia-BAI)] complex (tia-BAI = 1,3-bis(2’-thiazolylimino)isoindolinate(−)) was considered as a potential pre-catalyst for water oxidation providing the active form via the [...] Read more.
Pincer ligands occupy three coplanar sites at metal centers and often support both stability and reactivity. The five-coordinate [FeIIICl2(tia-BAI)] complex (tia-BAI = 1,3-bis(2’-thiazolylimino)isoindolinate(−)) was considered as a potential pre-catalyst for water oxidation providing the active form via the exchange of chloride ligands to water molecules. The tia-BAI pincer ligand renders water-insolubility to the Fe–(tia-BAI) assembly, but it tolerates the presence of water in acetone and produces electrocatalytic current in cyclic voltammetry associated with molecular water oxidation catalysis. Upon addition of water to [FeIIICl2(tia-BAI)] in acetone the changes in the Fe3+/2+ redox transition and the UV-visible spectra could be associated with solvent-dependent equilibria between the aqua and chloride complex forms. Immobilization of the complex from methanol on indium-tin-oxide (ITO) electrode by means of drop-casting resulted in water oxidation catalysis in borate buffer. The O2 detected by gas chromatography upon electrolysis at pH 8.3 indicates >80% Faraday efficiency by a TON > 193. The investigation of the complex/ITO assembly by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) before and after electrolysis, and re-dissolution tests suggest that an immobilized molecular catalyst is responsible for catalysis and de-activation occurs by depletion of the metal. Full article
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