Catalytic Applications of Transition Metals

Topic Information

Dear Colleagues,

Transition metal-containing compounds are very interesting and efficient catalysts, used for a wide range of chemical reactions. Accomplishing a high catalytic activity with relatively low metal loading is an outstanding advantage, generating low-cost and environmentally friendlier processes. Generally, catalysts are used as molecular or supported objects. Catalytic processes containing transition metal elements are of growing interest, notably heterogeneous ones, in terms of reuse and recycling. The Special Issue aims to highlight the recent advances in the development of transition metal-containing catalysts, including coordination complexes, polyoxoanions, metal clusters, or nanoparticles, and bulk materials (mesoporous materials, surfaces, etc.). The involvement of these elements in catalytic materials plays a role in the enhancement of catalytic performance. The emphasis is on recent trends, including materials processing (synthesis and characterization) and their catalytic applications, from simple reactions with model substrates to more complex and challenging ones. A mechanistic approach, linking the structure with the activity, would be highly appreciated. It is our pleasure to invite you to submit a manuscript to this Special Issue. Full papers, communications, and reviews are all welcome.

Dr. Dominique Agustin
Dr. Jana Pisk
Topic Editors

Keywords

Participating Journals

Journal Name	Impact Factor	CiteScore	Launched Year	First Decision (median)	APC
Alloys alloys	-	-	2022	22.5 Days	CHF 1000
Catalysts catalysts	3.8	6.8	2011	13.9 Days	CHF 2200
Materials materials	3.1	5.8	2008	13.9 Days	CHF 2600
Nanomaterials nanomaterials	4.4	8.5	2010	14.1 Days	CHF 2400
Molecules molecules	4.2	7.4	1996	15.1 Days	CHF 2700

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Published Papers (12 papers)

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29 pages, 7216 KiB  

Open AccessReview

Added Complexity!—Mechanistic Aspects of Heterobimetallic Complexes for Application in Homogeneous Catalysis

by Zeno Fickenscher and Evamarie Hey-Hawkins

Molecules 2023, 28(10), 4233; https://doi.org/10.3390/molecules28104233 - 22 May 2023

Cited by 8 | Viewed by 3052

Abstract

Inspired by multimetallic assemblies and their role in enzyme catalysis, chemists have developed a plethora of heterobimetallic complexes for application in homogeneous catalysis. Starting with small heterobimetallic complexes with σ-donating and π-accepting ligands, such as N-heterocyclic carbene and carbonyl ligands, more and more [...] Read more.

Inspired by multimetallic assemblies and their role in enzyme catalysis, chemists have developed a plethora of heterobimetallic complexes for application in homogeneous catalysis. Starting with small heterobimetallic complexes with σ-donating and π-accepting ligands, such as N-heterocyclic carbene and carbonyl ligands, more and more complex systems have been developed over the past two decades. These systems can show a significant increase in catalytic activity compared with their monometallic counterparts. This increase can be attributed to new reaction pathways enabled by the presence of a second metal center in the active catalyst. This review focuses on mechanistic aspects of heterobimetallic complexes in homogeneous catalysis. Depending on the type of interaction of the second metal with the substrates, heterobimetallic complexes can be subdivided into four classes. Each of these classes is illustrated with multiple examples, showcasing the versatility of both, the types of interactions possible, and the reactions accessible. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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11 pages, 2463 KiB  

Open AccessCommunication

Boosting Higher Selectivity for Thymol Hydrogenation Reaction over Ni/Ce Catalyst

by Haifang Mao, Yongqi Wu, Bo Cui, Yun Zhao and Xiang Zheng

Catalysts 2023, 13(5), 808; https://doi.org/10.3390/catal13050808 - 27 Apr 2023

Cited by 1 | Viewed by 1814

Abstract

The production of menthol via thymol hydrogenation is an industrial technology but is challenging due to the unsatisfied selectivity to menthol. Herein, Ni/Ce catalysts were prepared and used in thymol hydrogenation. A high selectivity of menthol was achieved over Ni₄/Ce₁ [...] Read more.

The production of menthol via thymol hydrogenation is an industrial technology but is challenging due to the unsatisfied selectivity to menthol. Herein, Ni/Ce catalysts were prepared and used in thymol hydrogenation. A high selectivity of menthol was achieved over Ni₄/Ce₁ catalysts under the optimized reaction condition. Ce incorporation can improve both the activity of Ni catalyst and the selectivity to menthol. To reveal the functions of Ce, catalyst characterizations were conducted. The catalytic activity improvement may be related to the remarkable increase in the surface area of the catalyst and the lower crystalline sizes of Ni that take place when a tiny amount of Ce is incorporated into Ni. Higher selectivity to menthol may be related to the modification of the acidity of an Ni catalyst. In addition, the stability of the Ni₄/Ce₁ catalysts was also evaluated, and after five recycles, the Ni₄/Ce₁ catalysts exhibited outstanding catalytic activity and stability. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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15 pages, 3043 KiB  

Open AccessArticle

Novel Catalyst Composites of Ni- and Co-Based Nanoparticles Supported on Inorganic Oxides for Fatty Acid Hydrogenations

by Ekaterina Mamontova, Corine Trabbia, Isabelle Favier, Alejandro Serrano-Maldonado, Jean-Bernard Ledeuil, Lénaïc Madec, Montserrat Gómez and Daniel Pla

Nanomaterials 2023, 13(9), 1435; https://doi.org/10.3390/nano13091435 - 22 Apr 2023

Cited by 4 | Viewed by 1705

Abstract

In the quest to develop nanometrically defined catalytic systems for applications in the catalytic valorization of agri-food wastes, small Ni-based nanoparticles supported on inorganic solid supports have been prepared by decomposition of organometallic precursors in refluxing ethanol under H₂ atmosphere, in the [...] Read more.

In the quest to develop nanometrically defined catalytic systems for applications in the catalytic valorization of agri-food wastes, small Ni-based nanoparticles supported on inorganic solid supports have been prepared by decomposition of organometallic precursors in refluxing ethanol under H₂ atmosphere, in the presence of supports exhibiting insulating or semi-conductor properties, such as MgAl₂O₄ and TiO₂, respectively. The efficiency of the as-prepared Ni-based nanocomposites has been evaluated towards the hydrogenation of unsaturated fatty acids under solvent-free conditions, with high selectivity regarding the hydrogenation of C=C bonds. The influence of the support on the catalytic performance of the prepared Ni-based nanocomposites is particularly highlighted. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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16 pages, 3049 KiB  

Open AccessArticle

Highly Efficient Copper Doping LaFeO₃ Perovskite for Bisphenol A Removal by Activating Peroxymonosulfate

by Xin Zhong, Junjie Liu, Haonan Jie, Wenting Wu and Fubin Jiang

Catalysts 2023, 13(3), 575; https://doi.org/10.3390/catal13030575 - 12 Mar 2023

Cited by 2 | Viewed by 2443

Abstract

A series of copper doping LaFeO₃ perovskite (LaCu_xFe_1−xO₃, LCFO, x = 0.1, 0.4, 0.5, 0.6, 0.9) are successfully synthesized by the sol-gel method under mild conditions. In this study, it is applied for the activation of [...] Read more.

A series of copper doping LaFeO₃ perovskite (LaCu_xFe_1−xO₃, LCFO, x = 0.1, 0.4, 0.5, 0.6, 0.9) are successfully synthesized by the sol-gel method under mild conditions. In this study, it is applied for the activation of peroxymonosulfate (PMS) for bisphenol A (BPA) removal. More than 92.6% of BPA was degraded within 30 min at 0.7 g/L of LCFO and 10.0 mM of PMS over a wide pH range with limited leaching of copper and iron ions. The physical–chemical properties of the catalysts were demonstrated by using X-ray diffraction (XRD), N₂ adsorption–desorption isotherms, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Furthermore, the effects of catalyst dosage, PMS concentration, initial pH value, and inorganic anions on the LCFO/PMS system were fully investigated. Quenching experiments were performed to verify the formation of reactive oxidant species, which showed that the radical reaction and mechanisms play a great role in the catalytic degradation of BPA. The perovskite LCFO is considered a stable, easy to synthesize, and efficient catalyst for the activation of PMS for wastewater treatment. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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20 pages, 2273 KiB  

Open AccessArticle

N-Arylation of 3-Formylquinolin-2(1H)-ones Using Copper(II)-Catalyzed Chan–Lam Coupling

by Jhesua Valencia, Oriel A. Sánchez-Velasco, Jorge Saavedra-Olavarría, Patricio Hermosilla-Ibáñez, Edwin G. Pérez and Daniel Insuasty

Molecules 2022, 27(23), 8345; https://doi.org/10.3390/molecules27238345 - 30 Nov 2022

Cited by 5 | Viewed by 2840

Abstract

3-formyl-2-quinolones have attracted the scientific community’s attention because they are used as versatile building blocks in the synthesis of more complex compounds showing different and attractive biological activities. Using copper-catalyzed Chan–Lam coupling, we synthesized 32 new N-aryl-3-formyl-2-quinolone derivatives at 80 °C, in [...] Read more.

3-formyl-2-quinolones have attracted the scientific community’s attention because they are used as versatile building blocks in the synthesis of more complex compounds showing different and attractive biological activities. Using copper-catalyzed Chan–Lam coupling, we synthesized 32 new N-aryl-3-formyl-2-quinolone derivatives at 80 °C, in air and using inexpensive phenylboronic acids as arylating agents. 3-formyl-2-quinolones and substituted 3-formyl-2-quinolones can act as substrates, and among the products, the p-methyl derivative 9a was used as a substrate to obtain different derivatives such as alcohol, amine, nitrile, and chalcone. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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15 pages, 2693 KiB  

Open AccessArticle

Silver Catalyzed Site-Selective C(sp³)−H Bond Amination of Secondary over Primary C(sp³)−H Bonds

by Luzhen Jiao, Dawei Teng, Zixuan Wang and Guorui Cao

Molecules 2022, 27(19), 6174; https://doi.org/10.3390/molecules27196174 - 21 Sep 2022

Cited by 1 | Viewed by 2016

Abstract

Sulfamates are widespread in numerous pharmacologically active molecules. In this paper, Silver/Bathophenanthroline catalyzed the intramolecular selective amination of primary C(sp³)−H bonds and secondary C(sp³)−H bonds of sulfamate esters, to produce cyclic sulfamates in good yields and with a high [...] Read more.

Sulfamates are widespread in numerous pharmacologically active molecules. In this paper, Silver/Bathophenanthroline catalyzed the intramolecular selective amination of primary C(sp³)−H bonds and secondary C(sp³)−H bonds of sulfamate esters, to produce cyclic sulfamates in good yields and with a high site-selectivity. DFT calculations revealed that the interaction between sulfamates and L10 makes the molecule more firmly attached to the catalyst, benefiting the catalysis reaction. The in vitro anticancer activity of the final products was evaluated in MCF-7 breast cancer cells. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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15 pages, 4299 KiB  

Open AccessEditor’s ChoiceArticle

Production of H₂-Free Carbon Monoxide from Formic Acid Dehydration: The Catalytic Role of Acid Sites in Sulfated Zirconia

by Hyun Ju Lee, Dong-Chang Kang, Eun-Jeong Kim, Young-Woong Suh, Dong-Pyo Kim, Haksoo Han and Hyung-Ki Min

Nanomaterials 2022, 12(17), 3036; https://doi.org/10.3390/nano12173036 - 1 Sep 2022

Cited by 8 | Viewed by 2717

Abstract

The formic acid (CH₂O₂) decomposition over sulfated zirconia (SZ) catalysts prepared under different synthesis conditions, such as calcination temperature (500–650 °C) and sulfate loading (0–20 wt.%), was investigated. Three sulfate species (tridentate, bridging bidentate, and pyrosulfate) on the SZ [...] Read more.

The formic acid (CH₂O₂) decomposition over sulfated zirconia (SZ) catalysts prepared under different synthesis conditions, such as calcination temperature (500–650 °C) and sulfate loading (0–20 wt.%), was investigated. Three sulfate species (tridentate, bridging bidentate, and pyrosulfate) on the SZ catalysts were characterized by using temperature-programmed decomposition (TPDE), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The acidic properties of the SZ catalysts were investigated by the temperature-programmed desorption of iso-propanol (IPA-TPD) and pyridine-adsorbed infrared (Py-IR) spectroscopy and correlated with their catalytic properties in formic acid decomposition. The relative contributions of Brønsted and Lewis acid sites to the formic acid dehydration were compared, and optimal synthetic conditions, such as calcination temperature and sulfate loading, were proposed. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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8 pages, 1579 KiB  

Open AccessArticle

Development of Novel Pyrolysis Technology Involving Chromium for the Measurement of D/H Ratios in n-Alkanes

by Lantian Xing, Zhongping Li, Yan Liu and Liwu Li

Catalysts 2022, 12(9), 950; https://doi.org/10.3390/catal12090950 - 26 Aug 2022

Cited by 1 | Viewed by 1729

Abstract

A new pyrolysis technology involving chromium is proposed for the determination of δD in alkanes based on the systematic analysis of reaction temperature, conversion rate, and reaction mechanism. Compared with the traditional high-temperature conversion (HTC) method, our findings suggest that chromium/high-temperature conversion (Cr/HTC) [...] Read more.

A new pyrolysis technology involving chromium is proposed for the determination of δD in alkanes based on the systematic analysis of reaction temperature, conversion rate, and reaction mechanism. Compared with the traditional high-temperature conversion (HTC) method, our findings suggest that chromium/high-temperature conversion (Cr/HTC) can improve the conversion rate of hydrocarbons and reduce the required pyrolysis temperature by up to 175 °C; meanwhile, the pyrolysis conversion rate of hydrocarbons increased by an average of 2.42% across the entire analyzed temperature range using the Cr/HTC method. Changes in the chromium wire itself were analyzed using X-ray photoelectron spectroscopy (XPS); this facilitated an understanding of the interaction mechanism between chromium and hydrocarbons and possible pathways of the catalytic pyrolysis process. The results show that chromium reacts with hydrocarbons, capturing carbon as chromium carbide (Cr₂C₃ and CrC₃) and releasing hydrogen in the form of H₂. As the reaction progresses, the resulting free carbon accumulates on the surface of the chromium wire or chromium carbide, resulting in a marked reduction in the Cr/C ratio; these findings provide reliable evidence for the further application of Cr/HTC technology. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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19 pages, 1740 KiB  

Open AccessArticle

Intrinsic Multienzyme-like Activities of the Nanoparticles of Mn and Fe Cyano-Bridged Assemblies

by Yunong Zhang, David Kudriashov, Liubov Pershina, Andreas Offenhäusser and Yulia Mourzina

Nanomaterials 2022, 12(12), 2095; https://doi.org/10.3390/nano12122095 - 17 Jun 2022

Cited by 7 | Viewed by 2469

Abstract

This study investigates the intrinsic multienzyme-like properties of the non-stabilized nanocrystalline nanoparticles of manganese-doped Prussian blue (Mn-PB) nanozymes and Prussian blue (PB) nanozymes in chemical and electrocatalytic transformations of reactive oxygen species. The effect of manganese doping on the structural, biomimetic, and electrocatalytic [...] Read more.

This study investigates the intrinsic multienzyme-like properties of the non-stabilized nanocrystalline nanoparticles of manganese-doped Prussian blue (Mn-PB) nanozymes and Prussian blue (PB) nanozymes in chemical and electrocatalytic transformations of reactive oxygen species. The effect of manganese doping on the structural, biomimetic, and electrocatalytic properties of cyano-bridged assemblies is also discussed. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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18 pages, 11972 KiB  

Open AccessArticle

Study of Ce, Ca, Fe, and Mn-Doped LaCoO₃ Perovskite Oxide for the Four-Way Purification of PM, NO_x, CO, and HC from Diesel Engine Exhaust

by Yinghui Wang, Xiurong Guo, Danfeng Du and Shaochi Yang

Materials 2022, 15(12), 4149; https://doi.org/10.3390/ma15124149 - 10 Jun 2022

Cited by 10 | Viewed by 2533

Abstract

Perovskite-type catalysts were widely used in the field of automobile exhaust purification due to their inherent physicochemical properties and excellent doping characteristics. A series of La_1−xM_xCo_1−yN_yO₃ (M = Ce, Ca; N = Fe, Mn) [...] Read more.

Perovskite-type catalysts were widely used in the field of automobile exhaust purification due to their inherent physicochemical properties and excellent doping characteristics. A series of La_1−xM_xCo_1−yN_yO₃ (M = Ce, Ca; N = Fe, Mn) perovskite-type catalyst samples were prepared by sol-gel method for the four-way purification of PM, NO_x, CO, and HC emitted by diesel exhaust. The activity of catalyst samples was tested by simulation experiments and hydrogen temperature-programmed reduction (H₂-TPR). Catalyst samples were characterized by means of XRD, FT-IR, SEM, BET, and XPS analysis. The results demonstrated that the perovskite-type catalyst samples with a particle pore size of 3–5 μm can be prepared by sol-gel method. When A-site of LaCoO₃ perovskite-type oxide was doped by cerium ions, the catalyst samples produced small distortion. The doping of cerium ions to A-site was more conducive to the four-way purification of diesel exhaust than calcium ions. La_0.8Ce_0.2CoO₃ perovskite-type samples showed the best purification efficiency, and the purification efficiencies of PM, NO_x, CO, and HC were 90%, 85%, 94%, and 100%, respectively. When the B-site of La_0.8Ce_0.2CoO₃ perovskite was doped with iron ions, the purification efficiency of catalyst samples for PM and NO_x can be further enhanced. When the B-site of La_0.8Ce_0.2CoO₃ perovskite was doped with manganese ions, the purification efficiency of the catalyst samples for PM can be further enhanced. It can be seen from the simulation experiments that La_0.8Ce_0.2Co_0.7Fe_0.3O₃ perovskite was the best doping amount, and the purification efficiencies of PM, NO_x, CO, and HC were 95%, 92%, 94%, and 100%, respectively. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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17 pages, 3166 KiB  

Open AccessArticle

The Scalable Solid-State Synthesis of a Ni₅P₄/Ni₂P–FeNi Alloy Encapsulated into a Hierarchical Porous Carbon Framework for Efficient Oxygen Evolution Reactions

by Xiangyun Tian, Peng Yi, Junwei Sun, Caiyun Li, Rongzhan Liu and Jian-Kun Sun

Nanomaterials 2022, 12(11), 1848; https://doi.org/10.3390/nano12111848 - 28 May 2022

Cited by 6 | Viewed by 2605

Abstract

The exploration of high-performance and low-cost electrocatalysts towards the oxygen evolution reaction (OER) is essential for large-scale water/seawater splitting. Herein, we develop a strategy involving the in situ generation of a template and pore-former to encapsulate a Ni₅P₄/Ni₂ [...] Read more.

The exploration of high-performance and low-cost electrocatalysts towards the oxygen evolution reaction (OER) is essential for large-scale water/seawater splitting. Herein, we develop a strategy involving the in situ generation of a template and pore-former to encapsulate a Ni₅P₄/Ni₂P heterojunction and dispersive FeNi alloy hybrid particles into a three-dimensional hierarchical porous graphitic carbon framework (labeled as Ni₅P₄/Ni₂P–FeNi@C) via a room-temperature solid-state grinding and sodium-carbonate-assisted pyrolysis method. The synergistic effect of the components and the architecture provides a large surface area with a sufficient number of active sites and a hierarchical porous pathway for efficient electron transfer and mass diffusion. Furthermore, a graphitic carbon coating layer restrains the corrosion of alloy particles to boost the long-term durability of the catalyst. Consequently, the Ni₅P₄/Ni₂P–FeNi@C catalyst exhibits extraordinary OER activity with a low overpotential of 242 mV (10 mA cm⁻²), outperforming the commercial RuO₂ catalyst in 1 M KOH. Meanwhile, a scale-up of the Ni₅P₄/Ni₂P–FeNi@C catalyst created by a ball-milling method displays a similar level of activity to the above grinding method. In 1 M KOH + seawater electrolyte, Ni₅P₄/Ni₂P–FeNi@C also displays excellent stability; it can continuously operate for 160 h with a negligible potential increase of 2 mV. This work may provide a new avenue for facile mass production of an efficient electrocatalyst for water/seawater splitting and diverse other applications. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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16 pages, 2118 KiB  

Open AccessArticle

Degradation of Benzotriazole UV Stabilizers in PAA/d-Electron Metal Ions Systems—Removal Kinetics, Products and Mechanism Evaluation

by Dariusz Kiejza, Joanna Karpińska and Urszula Kotowska

Molecules 2022, 27(10), 3349; https://doi.org/10.3390/molecules27103349 - 23 May 2022

Cited by 17 | Viewed by 3833

Abstract

Benzotriazole UV stabilizers (BUVs) have gained popularity, due to their absorption properties in the near UV range (200–400 nm). They are used in the technology for manufacturing plastics, protective coatings, and cosmetics, to protect against the destructive influence of UV radiation. These compounds [...] Read more.

Benzotriazole UV stabilizers (BUVs) have gained popularity, due to their absorption properties in the near UV range (200–400 nm). They are used in the technology for manufacturing plastics, protective coatings, and cosmetics, to protect against the destructive influence of UV radiation. These compounds are highly resistant to biological and chemical degradation. As a result of insufficient treatment by sewage treatment plants, they accumulate in the environment and in the tissues of living organisms. BUVs have adverse effects on living organisms. This work presents the use of peracetic acid in combination with d-electron metal ions (Fe²⁺, Co²⁺), for the chemical oxidation of five UV filters from the benzotriazole group: 2-(2-hydroxy-5-methylphenyl)benzotriazole (UV-P), 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (UV-326), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol (UV-327), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV-328), and 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (UV-329). The oxidation procedure has been optimized based on the design of experiments (DoE) methodology. The oxidation of benzotriazoles follows first order kinetics. The oxidation products of each benzotriazole were investigated, and the oxidation mechanisms of the tested compounds were proposed. Full article

(This article belongs to the Topic Catalytic Applications of Transition Metals)

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