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Inorganics, Volume 8, Issue 11 (November 2020) – 6 articles

Cover Story (view full-size image): The novel compounds [Zn(tr2ad)Cl2]n, {[Cu(tr2ad)Cl]Cl∙4H2O}n, [Cd2(tr2ad)Cl4]n, {[Cu(tr2ad)(NO3)](NO3)}n and {[Cd(tr2ad)(NO3)](NO3)∙H2O}n (tr2ad = 1,3-bis(1,2,4-triazol-4-yl)adamantane) enlarge the family of tr2ad-based coordination polymers (CPs) and contribute to highlighting both the versatility of the tr2ad spacer, in terms of coordination modes, and the variability in the crystal structure dimensionality of the corresponding CPs. View this paper.
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Open AccessErratum
Erratum: Hadjixenophontos, E.; et al. A Review of the MSCA ITN ECOSTORE—Novel Complex Metal Hydrides for Efficient and Compact Storage of Renewable Energy as Hydrogen and Electricity. Inorganics 2020, 8, 17
Inorganics 2020, 8(11), 63; https://doi.org/10.3390/inorganics8110063 - 18 Nov 2020
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Abstract
The authors wish to make the following corrections to this paper [...] Full article
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Open AccessReview
Redox-Active Manganese Pincers for Electrocatalytic CO2 Reduction
Inorganics 2020, 8(11), 62; https://doi.org/10.3390/inorganics8110062 - 11 Nov 2020
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Abstract
The decrease of total amount of atmospheric CO2 is an important societal challenge in which CO2 reduction has an important role to play. Electrocatalytic CO2 reduction with homogeneous catalysts is based on highly tunable catalyst design and exploits an abundant [...] Read more.
The decrease of total amount of atmospheric CO2 is an important societal challenge in which CO2 reduction has an important role to play. Electrocatalytic CO2 reduction with homogeneous catalysts is based on highly tunable catalyst design and exploits an abundant C1 source to make valuable products such as fuels and fuel precursors. These methods can also take advantage of renewable electricity as a green reductant. Mn-based catalysts offer these benefits while incorporating a relatively cheap and abundant first-row transition metal. Historically, interest in this field started with Mn(bpy-R)(CO)3X, whose performance matched that of its Re counterparts while achieving substantially lower overpotentials. This review examines an emerging class of homogeneous Mn-based electrocatalysts for CO2 reduction, Mn complexes with meridional tridentate coordination also known as Mn pincers, most of which contain redox-active ligands that enable multi-electron catalysis. Although there are relatively few examples in the literature thus far, these catalysts bring forth new catalytic mechanisms not observed for the well-established Mn(bpy-R)(CO)3X catalysts, and show promising reactivity for future studies. Full article
(This article belongs to the Special Issue Organomanganese Chemistry)
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Open AccessArticle
Hydrosilylation of Aldehydes by a Manganese α-Diimine Complex
Inorganics 2020, 8(11), 61; https://doi.org/10.3390/inorganics8110061 - 10 Nov 2020
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Abstract
This paper describes the catalytic activity of air stable and easy to handle manganese complexes towards the hydrosilylation of aldehydes. These catalysts incorporate a bulky diazabutadiene ligand and exhibit good functional group tolerance and chemoselectivity in the hydrosilylation of aldehydes, utilizing primary silanes [...] Read more.
This paper describes the catalytic activity of air stable and easy to handle manganese complexes towards the hydrosilylation of aldehydes. These catalysts incorporate a bulky diazabutadiene ligand and exhibit good functional group tolerance and chemoselectivity in the hydrosilylation of aldehydes, utilizing primary silanes as the reducing agent. The reactions proceed with turnover frequencies approaching 150 h−1 in some instances, similar to those observed for other manganese-based catalysts. The conversion of aromatic aldehydes to the corresponding alcohols was found to be more efficient than that for the analogous aliphatic systems. Full article
(This article belongs to the Special Issue Organomanganese Chemistry)
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Open AccessArticle
New Coordination Polymers of Zinc(II), Copper(II) and Cadmium(II) with 1,3-Bis(1,2,4-triazol-4-yl)adamantane
Inorganics 2020, 8(11), 60; https://doi.org/10.3390/inorganics8110060 - 06 Nov 2020
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Abstract
The new coordination polymers (CPs) [Zn(tr2ad)Cl2]n, {[Cu(tr2ad)Cl]Cl∙4H2O}n, [Cd2(tr2ad)Cl4]n, {[Cu(tr2ad)(NO3)](NO3)}n and {[Cd(tr2ad)(NO3)](NO3 [...] Read more.
The new coordination polymers (CPs) [Zn(tr2ad)Cl2]n, {[Cu(tr2ad)Cl]Cl∙4H2O}n, [Cd2(tr2ad)Cl4]n, {[Cu(tr2ad)(NO3)](NO3)}n and {[Cd(tr2ad)(NO3)](NO3)∙H2O}n were obtained in the form of air- and moisture-stable microcrystalline powders by the solvothermal reactions of zinc(II), copper(II) and cadmium(II) chlorides or nitrates with the ligand 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr2ad). Investigation of the thermal behaviour assessed the thermal stability of these CPs, with [Cd2(tr2ad)Cl4]n starting to decompose only around 365 °C. As retrieved by powder X-ray diffraction, while [Zn(tr2ad)Cl2]n features 1-D chains along which the metal centre shows a tetrahedral geometry and the spacer is exo-bidentate, the other CPs contain 2-D double-layers in which the metal ions possess an octahedral stereochemistry and the linker is exo-tetradentate. A comparative structural analysis involving known coordination compounds containing the tr2ad ligand enabled us to disclose (i) the versatility of the ligand, as far as the coordination modes are concerned; (ii) the variability in crystal structure dimensionality, ranging from 1-D to 3-D; (iii) the fact that, to the best of our knowledge, [Zn(tr2ad)Cl2]n is the first ZnII-based CP containing the tr2ad spacer. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Open AccessArticle
Toward Overcoming the Challenges in the Comparison of Different Pd Nanocatalysts: Case Study of the Ethanol Oxidation Reaction
Inorganics 2020, 8(11), 59; https://doi.org/10.3390/inorganics8110059 - 28 Oct 2020
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Abstract
Precious metal nanoparticles, in particular palladium nanomaterials, show excellent catalytic properties and are key in the development of energy systems. For instance, ethanol fuel cells are promising devices for sustainable energy conversion, where Pd-based catalysts are key catalysts for the related ethanol oxidation [...] Read more.
Precious metal nanoparticles, in particular palladium nanomaterials, show excellent catalytic properties and are key in the development of energy systems. For instance, ethanol fuel cells are promising devices for sustainable energy conversion, where Pd-based catalysts are key catalysts for the related ethanol oxidation reaction (EOR). Pd is a limited resource; thus, a remaining challenge is the development of efficient and stable Pd-based catalysts. This calls for a deeper understanding of the Pd properties at the nanoscale. This knowledge can be gained in comparative studies of different Pd nanomaterials. However, such studies remain challenging to perform and interpret due to the lack of cross-studies using the same Pd nanomaterials as a reference. Here, as-prepared sub 3 nm diameter surfactant-free Pd nanoparticles supported on carbon are obtained by a simple approach. The as-prepared catalysts with Pd loading 10 and 30 wt % show higher activity and stability compared to commercially available counterparts for the EOR. Upon electrochemical testing, a significant size increase and loss of electrochemical active surface are observed for the as-prepared catalysts, whereas the commercial samples show an increase in the electrochemically active surface area and moderate size increase. This study shines light on the challenging comparison of different catalysts across the literature. Further advancement in Pd (electro)catalyst design will gain from including self-prepared catalysts. The simple synthesis detailed easily leads to suitable nanoparticles to be used as a reference for more systematic comparative studies of Pd catalysts across the literature. Full article
(This article belongs to the Special Issue Palladium Catalysts: From Design to Applications)
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Open AccessEditorial
Beyond Hydrogen Storage—Metal Hydrides as Multifunctional Materials for Energy Storage and Conversion
Inorganics 2020, 8(11), 58; https://doi.org/10.3390/inorganics8110058 - 23 Oct 2020
Viewed by 406
Abstract
Following the E-MRS (European Materials Research Society) fall meeting 2019, Symposium L, this Special Issue of Inorganics, entitled “Beyond Hydrogen Storage—Metal Hydrides as Multifunctional Materials for Energy Storage and Conversion”, is dedicated to the wide range of emerging energy-related inorganic hydrogen-containing materials [...] Read more.
Following the E-MRS (European Materials Research Society) fall meeting 2019, Symposium L, this Special Issue of Inorganics, entitled “Beyond Hydrogen Storage—Metal Hydrides as Multifunctional Materials for Energy Storage and Conversion”, is dedicated to the wide range of emerging energy-related inorganic hydrogen-containing materials [...] Full article
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