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Chemistry
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Earth-Abundant Metal Chemistry and Catalysis
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Earth-Abundant Metal Chemistry and Catalysis

A special issue of Chemistry (ISSN 2624-8549). This special issue belongs to the section "Catalysis".

Deadline for manuscript submissions: closed (30 September 2022) | Viewed by 16293

Special Issue Editor

Dr. Guoqi Zhang

E-Mail Website
Guest Editor
Department of Sciences, John Jay College and PhD in Chemistry Program, The Graduate Center of the City University of New York, New York, NY 10019, USA
Interests: design of new catalysts with terpyridine ligands; earth-abundant metal catalysis; organometallic chemistry and small molecule activation; coordination polymers for catalytic applications; metallic anticancer drug design and synthesis

Special Issue Information

Dear Colleagues,

As the new MDPI flagship journal Chemistry (ISSN 2624-8549) is formally launched, we are excited to open this Special issue with a theme of Earth-Abundant Metal Chemistry and Catalysis. Currently, there is an explosively increasing amount of interest in sustainable chemistry and molecular catalysis with earth-abundant metals within the synthesis and catalysis communities. A themed issue on this topic is necessary and anticipated to attract significant contributions.

It is currently of urgency to replace noble metal catalysts with earth-abundant, inexpensive alternatives in many aspects, including valuable organic transformations, small molecule activation, and energy conversion. Rational design of molecular catalysts is the key to enabling the reactivity and hence catalytic activity. In this issue, we welcome submissions of work related to the synthesis, structure, and reactivity of molecular complexes involving earth-abundant metals as well as their catalytic applications in both traditional and new organic reactions, small molecule (CO2, CO, N2, etc.) activation, and biomass conversion. Experimental and theoretical studies leading to mechanistic understanding are particularly encouraged. In addition, submissions from a broader area of catalysis such as electrocatalysis, photocatalysis, and nanocatalysis that involve the use of earth-abundant metals are also welcomed.

Dr. Guoqi Zhang
Guest Editor

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. Chemistry is an international peer-reviewed open access semimonthly 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 1800 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

  • Catalyst design
  • Well-defined molecular catalysts
  • Nanocatalysts
  • Earth-abundant metal catalysis
  • Sustainable chemistry
  • Green catalysis
  • Biomass conversion
  • Small molecule activation

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Further information on MDPI's Special Issue polices can be found here.

Published Papers (5 papers)

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Research

16 pages, 3148 KiB  
Article
Spectrophotometric Determination of Formation Constants of Iron(III) Complexes with Several Ligands
by José J. N. Segoviano-Garfias, Gabriela A. Zanor, Fidel Ávila-Ramos, Egla Yareth Bivián-Castro and Carlos A. Rubio-Jiménez
Chemistry 2022, 4(3), 701-716; https://doi.org/10.3390/chemistry4030050 - 15 Jul 2022
Cited by 4 | Viewed by 3725
Abstract
Dye-sensitized solar cells transform solar light into electricity. One commonly used dye is a ruthenium complex. However, the use of ruthenium has been shown to have several disadvantages. In this study, via singular spectrum analysis using HypSpec software, we determined the formation constants [...] Read more.
Dye-sensitized solar cells transform solar light into electricity. One commonly used dye is a ruthenium complex. However, the use of ruthenium has been shown to have several disadvantages. In this study, via singular spectrum analysis using HypSpec software, we determined the formation constants and calculated individual electronic spectra of species of iron(III) with several ligands (1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 2,2′-bipyridyl, 5,5-dimethyl-2,2′-bipyridyl, 4,4′-di-tert-butyl-2,2′-bipyridyl, 1,10-phenanthroline, and 3,4,7,8-tetramethyl-1,10-phenanthroline) in methanol solution. We present a spectral comparison of the complexes reported here to the ruthenium complex: tris-(2,2′-bipyridyl)ruthenium(II). Full article
(This article belongs to the Special Issue Earth-Abundant Metal Chemistry and Catalysis)
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16 pages, 3729 KiB  
Article
Copper(II) NHC Catalyst for the Formation of Phenol from Arylboronic Acid
by Mitu Sharma, Bhupendra Adhikari, Raymond Femi Awoyemi, Amanda M. Perkins, Alison K. Duckworth, Bruno Donnadieu, David O. Wipf, Sean L. Stokes and Joseph P. Emerson
Chemistry 2022, 4(2), 560-575; https://doi.org/10.3390/chemistry4020040 - 7 Jun 2022
Cited by 8 | Viewed by 3652
Abstract
Arylboronic acids are commonly used in modern organic chemistry to form new C–C and C–heteroatom bonds. These activated organic synthons show reactivity with heteroatoms in a range of substrates under ambient oxidative conditions. This broad reactivity has limited their use in protic, renewable [...] Read more.
Arylboronic acids are commonly used in modern organic chemistry to form new C–C and C–heteroatom bonds. These activated organic synthons show reactivity with heteroatoms in a range of substrates under ambient oxidative conditions. This broad reactivity has limited their use in protic, renewable solvents like water, ethanol, and methanol. Here, we report our efforts to study and optimize the activation of arylboronic acids by a copper(II) N-heterocyclic carbene (NHC) complex in aqueous solution and in a range of alcohols to generate phenol and aryl ethers, respectively. The optimized reactivity showcases the ability to make targeted C–O bonds, but also identifies conditions where water and alcohol activation could be limiting for C–C and C–heteroatom bond-forming reactions. This copper(II) complex shows strong reactivity toward arylboronic acid activation in aqueous medium at ambient temperature. The relationship between product formation and temperature and catalyst loading are described. Additionally, the effects of buffer, pH, base, and co-solvent are explored with respect to phenol and ether generation reactions. Characterization of the new copper(II) NCN-pincer complex by X-ray crystallography, HR-MS, cyclic voltammetry, FT-IR and UV-Vis spectral studies is reported. Full article
(This article belongs to the Special Issue Earth-Abundant Metal Chemistry and Catalysis)
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14 pages, 3948 KiB  
Article
Influence of the Support Composition on the Activity of Cobalt Catalysts Supported on Hydrotalcite-Derived Mg-Al Mixed Oxides in Ammonia Synthesis
by Magdalena Zybert, Hubert Ronduda, Aleksandra Dziewulska, Kamil Sobczak, Andrzej Ostrowski, Wojciech Patkowski and Wioletta Raróg-Pilecka
Chemistry 2022, 4(2), 480-493; https://doi.org/10.3390/chemistry4020035 - 17 May 2022
Cited by 1 | Viewed by 2298
Abstract
Recently, catalysts with hydrotalcites and hydrotalcite-derived compounds have attracted particular interest due to their specific properties, mostly well-developed texture, high thermal stability, and favorable acid–base properties. In this work, we report the investigation of ammonia synthesis on barium-promoted cobalt catalysts supported on hydrotalcite-derived [...] Read more.
Recently, catalysts with hydrotalcites and hydrotalcite-derived compounds have attracted particular interest due to their specific properties, mostly well-developed texture, high thermal stability, and favorable acid–base properties. In this work, we report the investigation of ammonia synthesis on barium-promoted cobalt catalysts supported on hydrotalcite-derived Mg-Al mixed oxides with different Mg/Al molar ratios. The obtained catalysts were characterized using TGA-MS, nitrogen physisorption, XRPD, TEM, STEM-EDX, H2-TPD, CO2-TPD, and tested in ammonia synthesis (470 °C, 6.3 MPa, H2/N2 = 3). The studies revealed that the prepared Mg-Al mixed oxides are good candidates as support materials for Co-based catalysts. However, interestingly, the support composition does not influence the activity of Ba/Co/Mg-Al catalysts. The change in Mg/Al molar ratio in the range of 2–5 did not significantly change the catalyst properties. All the catalysts are characterized by similar textural, structural, and chemisorption properties. The similar density of basic sites on the surface of the studied catalysts was reflected in their comparable performance in ammonia synthesis. Full article
(This article belongs to the Special Issue Earth-Abundant Metal Chemistry and Catalysis)
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12 pages, 13309 KiB  
Article
Assembly of a 3D Cobalt(II) Supramolecular Framework and Its Applications in Hydrofunctionalization of Ketones and Aldehydes
by Guoqi Zhang, Alex Wang, Haisu Zeng, Shengping Zheng and Michelle C. Neary
Chemistry 2022, 4(2), 393-404; https://doi.org/10.3390/chemistry4020029 - 28 Apr 2022
Cited by 1 | Viewed by 2881
Abstract
A ditopic nitrogen ligand (E)-N′-(pyridin-4-ylmethylene)isonicotinohydrazide (L) containing both divergent pyridyl coordination sites and a hydrogen-bonding hydrazide–hydrazone moiety was synthesized. The Co(NCS)2-mediated self-assembly of L has resulted in the synthesis of a novel 3-dimensional (3D) supramolecular [...] Read more.
A ditopic nitrogen ligand (E)-N′-(pyridin-4-ylmethylene)isonicotinohydrazide (L) containing both divergent pyridyl coordination sites and a hydrogen-bonding hydrazide–hydrazone moiety was synthesized. The Co(NCS)2-mediated self-assembly of L has resulted in the synthesis of a novel 3-dimensional (3D) supramolecular framework (1) that features both coordination and hydrogen bonding interactions. X-ray structural analysis reveals the formation and coordination mode of 1 in the solid state. The rational utilization of coordination bonds and hydrogen bonding interactions is confirmed and responsible for constructing the 3D materials. Catalytic studies using 1 in the presence of an activator are performed for the hydroboration and hydrosilylation reactions of ketones and aldehydes, and the results are compared with previously reported cobalt-based polymeric catalysts. Full article
(This article belongs to the Special Issue Earth-Abundant Metal Chemistry and Catalysis)
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13 pages, 3821 KiB  
Article
Wasteless Synthesis and Properties of Highly Dispersed MgAl2O4 Based on Product of Thermal Activation of Gibbsite
by Aleksey V. Zhuzhgov, Vasily Y. Kruglyakov, Tatyana S. Glazneva, Evgeny A. Suprun and Lyubov A. Isupova
Chemistry 2022, 4(2), 316-328; https://doi.org/10.3390/chemistry4020024 - 11 Apr 2022
Cited by 1 | Viewed by 2202
Abstract
The study showed that the interaction of the product of centrifugal thermal activation of gibbsite with an aqueous solution of magnesium nitrate at a cationic ratio Mg:Al = 1:2 leads to the formation of mixed double hydroxides both under hydrothermal treatment at 150 [...] Read more.
The study showed that the interaction of the product of centrifugal thermal activation of gibbsite with an aqueous solution of magnesium nitrate at a cationic ratio Mg:Al = 1:2 leads to the formation of mixed double hydroxides both under hydrothermal treatment at 150 °C and at room temperature. The subsequent thermal treatment at 550 °C of the product of mild interaction leads to ~90% alumina-magnesia spinel and ~10% MgO, while the treatment of the hydrothermal interaction product leads to ~100% spinel with the stoichiometric composition MgAl2O4. The obtained spinel samples possess a high specific surface area (above 100 m2/g) and a hierarchical pore structure formed by the micron-level particles of different sizes (1–2 and 10–20 μm) consisting of ~70 nm crystallites with ~3 nm pores; the samples differ mostly in the total volume and quantitative ratio of the pores. The samples have Lewis acid sites of moderate strength on the surface, the amount of which is much lower to how it is when compared with a sample prepared by precipitation in that they also differ by quantity from each other as well (503 μmol/g for stoichiometric spinel and 304 μmol/g for sample with admixture of MgO). As the calcination temperature is raised to 850 °C, the acidity decreases—only weak Lewis acid sites are observed, the amount of which is also higher for stoichiometric spinel (161 and 39 μmol/g, respectively). The method proposed for the synthesis of alumina-magnesia systems provides a high dispersion and a much lower surface acidity for the oxides; in addition, it minimizes or completely excludes wash water, in distinction to the precipitation method. Full article
(This article belongs to the Special Issue Earth-Abundant Metal Chemistry and Catalysis)
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