Catalysis with Earth-Abundant Metals Iron, Cobalt, Nickel and Copper for Sustainability

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

Deadline for manuscript submissions: closed (28 February 2023) | Viewed by 7844

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Instituto Superior Técnico, Universidade de Lisboa, Centro de Química Estrutural, Lisboa, Portugal
Interests: catalysis (homogeneous catalysis, organoctalysis); organic synthesis; nanochemistry

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1. Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
2. Departamento de Engenharia Química, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1, 1959-007 Lisboa, Portugal
Interests: homogeneous catalysis; oxidation reactions; molecular electrochemistry; mechanochemistry; microwave-assisted reactions
Special Issues, Collections and Topics in MDPI journals

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Centro de Química Estrutural e Departamento de Engenharia Química, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Interests: green chemistry; innovative product design; sustainable processes; functionalized materials (in particular, involving C-scorpionates); catalysis (homogeneous, supported or nano- catalysis); electrochemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

For many years, the field of catalysis has been dominated by the utilization of platinum group metals (ruthenium, rhodium, palladium, osmium, iridium and platinum) as catalysts since, due to their capability to exist in many oxidation states, they have the most suitable properties. These include the ability to form complexes with many reagents and to catalyze reactions under milder conditions and with higher selectivity than many other metals, good functional-group tolerance, and also the fact that their synthetic chemistry is now highly understood. However, platinum group metals are among the rarest in the periodic table, being, therefore, less available, more expensive, and also toxic. Today, there is a shift in attention toward the more abundant first row-transition metals, i.e., iron, cobalt, nickel, and copper, as catalysts, for a more sustainable approach to synthesis. They are cheaper and less toxic, and a large wealth of reactions are continuously being reported, which these metals and their complexes are capable of catalyzing, often without the requirement for the use of inert atmospheres and sometimes even in water. In this issue of Catalysts, we aim to highlight this topic and bring to our readers the latest information available.

Dr. Ana Maria Faísca Phillips
Prof. Dr. Elisabete C.B.A. Alegria
Prof. Dr. Luísa Margarida Martins
Guest Editors

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Keywords

  • homogeneous catalysis
  • cooperative catalysis
  • green chemistry
  • sustainability
  • synthesis
  • reaction mechanisms
  • nanocatalysts

Published Papers (4 papers)

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Research

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12 pages, 10138 KiB  
Article
Green Catalytic Conversion of Some Benzylic Alcohols to Acids by NiO2 Nanoparticles (NPNPs) in Water
by Abdel Ghany F. Shoair, Mai M. A. H. Shanab, Nasser A. El-Ghamaz, Mortaga M. Abou-Krisha, Sayed H. Kenawy and Tarek A. Yousef
Catalysts 2023, 13(4), 645; https://doi.org/10.3390/catal13040645 - 23 Mar 2023
Cited by 2 | Viewed by 1349
Abstract
The aqueous basic systems NiSO4·6H2O/K2S2O8 (pH = 14) and NiSO4·6H2O/KBrO3 (pH = 11.5) were investigated for the catalytic conversion of benzyl alcohol and some para-substituted benzyl alcohols to their [...] Read more.
The aqueous basic systems NiSO4·6H2O/K2S2O8 (pH = 14) and NiSO4·6H2O/KBrO3 (pH = 11.5) were investigated for the catalytic conversion of benzyl alcohol and some para-substituted benzyl alcohols to their corresponding acids in 75–97% yields at room temperature. The active species was isolated and characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction, EDX and FT-IR techniques, and identified as comprising NiO2 nanoparticles (NPNPs). The SEM and TEM images of the Ni peroxide samples showed a fine spherical-like aggregation of NiO2 molecules with a nearly homogeneous partial size and confirmed the aggregation’s size to be in the range of 2–3 nm. The yields, turn over (TO) and turn over frequencies (TOF) were calculated. It was noticed that the aromatic alcohols containing para-substituted electron donation groups gave better yields than those having electron withdrawing groups. The optimum conditions for this catalytic reaction were studied using benzyl alcohol as a model. The mechanism of the catalytic conversion reaction was suggested, in which the produced NPNPs convert alcohols to acids in two steps through the formation of the corresponding aldehyde. The produced NiO because of this conversion is converted again to NPNPs by the excess of K2S2O8 or KBrO3. This catalytic cycle continues until all of the substrate is oxidized. Full article
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21 pages, 4589 KiB  
Article
Nickel-Copper Oxide Catalysts Deposited on Stainless Steel Meshes by Plasma Jet Sputtering: Comparison with Granular Analogues and Synergistic Effect in VOC Oxidation
by Květa Jirátová, Petr Soukal, Anna Kapran, Timur Babii, Jana Balabánová, Martin Koštejn, Martin Čada, Jaroslav Maixner, Pavel Topka, Zdeněk Hubička and František Kovanda
Catalysts 2023, 13(3), 595; https://doi.org/10.3390/catal13030595 - 16 Mar 2023
Cited by 5 | Viewed by 1743
Abstract
A novel method for the preparation of Ni-Cu oxide catalysts—deposition on stainless steel meshes using hollow cathode plasma jet sputtering—was studied. This method allows the preparation of thin oxide films. Consequently, the whole volume of the active phase is readily accessible for the [...] Read more.
A novel method for the preparation of Ni-Cu oxide catalysts—deposition on stainless steel meshes using hollow cathode plasma jet sputtering—was studied. This method allows the preparation of thin oxide films. Consequently, the whole volume of the active phase is readily accessible for the reactants and can be employed in the catalytic reaction due to the negligible effect of internal diffusion. As a result, the activity of our sputtered catalyst was seven times higher in ethanol oxidation and 61 times higher in toluene oxidation than that of the corresponding granular catalyst. Moreover, due to stainless steel meshes used as a catalyst support, the pressure drop across the catalyst bed was lower. Finally, the catalytic activity of the sputtered Ni-Cu oxide catalyst with Ni:Cu molar ratio of 1:1 in ethanol oxidation was 1.7 times higher than that of the commercial EnviCat® VOC-1544 catalyst, while the amount of the active phase in the catalyst bed was 139 times lower. The outstanding performance of the Ni0.5Cu0.5 catalyst was ascribed to the synergistic effect between the copper and nickel components. Full article
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Review

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53 pages, 77216 KiB  
Review
Non-Noble Metal Aromatic Oxidation Catalysis: From Metalloenzymes to Synthetic Complexes
by Eduard Masferrer-Rius and Robertus J. M. Klein Gebbink
Catalysts 2023, 13(4), 773; https://doi.org/10.3390/catal13040773 - 19 Apr 2023
Cited by 2 | Viewed by 2383
Abstract
The development of selective aromatic oxidation catalysts based on non-noble metals has emerged over the last decades, mainly due to the importance of phenol products as intermediates for the generation of pharmaceuticals or functional polymers. In nature, metalloenzymes can perform a wide variety [...] Read more.
The development of selective aromatic oxidation catalysts based on non-noble metals has emerged over the last decades, mainly due to the importance of phenol products as intermediates for the generation of pharmaceuticals or functional polymers. In nature, metalloenzymes can perform a wide variety of oxidative processes using molecular oxygen, including arene oxidations. However, the implementation of such enzymes in the chemical industry remains challenging. In this context, chemists have tried to mimic nature and design synthetic non-noble metal catalysts inspired by these enzymes. This review aims at providing a general overview of aromatic oxidation reactions catalyzed by metalloenzymes as well as synthetic first-row transition-metal complexes as homogeneous catalysts. The enzymes and complexes discussed in this review have been classified based on the transition-metal ion present in their active site, i.e., iron, copper, nickel, and manganese. The main points of discussion focus on enzyme structure and function, catalyst design, mechanisms of operation in terms of oxidant activation and substrate oxidation, and substrate scope. Full article
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21 pages, 7081 KiB  
Review
Tunable Late-Transition-Metal-Catalyzed Polymerization for Controlled Polymer Synthesis
by Hongyi Suo, Zisheng Zhang, Rui Qu, Yanan Gu and Yusheng Qin
Catalysts 2023, 13(4), 670; https://doi.org/10.3390/catal13040670 - 29 Mar 2023
Cited by 2 | Viewed by 1651
Abstract
As a powerful protocol for the preparation of common polymers, such as polyolefins, polyesters, and polycarbonates, late-transition-metal-catalyzed polymerization can be carried out by controlling the reaction conditions or developing dynamic catalytic systems that use external stimuli to influence the performance of the active [...] Read more.
As a powerful protocol for the preparation of common polymers, such as polyolefins, polyesters, and polycarbonates, late-transition-metal-catalyzed polymerization can be carried out by controlling the reaction conditions or developing dynamic catalytic systems that use external stimuli to influence the performance of the active sites, resulting in well-defined polymeric materials. In particularly, under the latter conditions, ‘one catalyst’ can provide more than one kind of polymer with a controlled sequence from the monomer mixture, making full use of the prepared catalyst. In this review, tunable modes, including reaction conditions, redox, light or electrochemical properties, Lewis acids, and alkali metal cations, of late-transition-metal-complex (especially iron, cobalt, and nickel)-catalyzed polymerization were collected and thoroughly discussed. Full article
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