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Inorganics
Volume 7
Issue 6
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Inorganics, Volume 7, Issue 6 (June 2019) – 11 articles

Cover Story (view full-size image): Shedding light on the bonding situation in an alkaline metal rare-earth metal silver telluride, density functional theory-based methods have been used to reveal the nature of bonding in RbPr2Ag3Te5. The crystal structure of the telluride is composed of tunnels, which are assembled by the tellurium atoms and encompass rubidium, praseodymium, and silver atoms. Between the silver atoms of neighboring [Ag@Te4] tetrahedrons, there are short Ag–Ag contacts, which are disregarded by applications of the Zintl–Klemm concept. View this paper.
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12 pages, 2476 KiB  
Article
Self-Assembled Monolayers of Molybdenum Sulfide Clusters on Au Electrode as Hydrogen Evolution Catalyst for Solar Water Splitting
by Stephanie Spring, Pravin S. Shinde, Patricia R. Fontenot, James P. Donahue and Shanlin Pan
Inorganics 2019, 7(6), 79; https://doi.org/10.3390/inorganics7060079 - 25 Jun 2019
Cited by 4 | Viewed by 4835
Abstract
Hydrogen evolution reaction (HER) activities of self-assembled monolayers (SAMs) of [Mo3S7(S2CNMe2)3] and several other MoSx molecular clusters are presented on planer Au electrode. Our study suggests that such Mo-S clusters are unstable [...] Read more.
Hydrogen evolution reaction (HER) activities of self-assembled monolayers (SAMs) of [Mo3S7(S2CNMe2)3] and several other MoSx molecular clusters are presented on planer Au electrode. Our study suggests that such Mo-S clusters are unstable under HER reaction conditions of a strongly acidic electrolyte. The [Mo3S7(S2CNEt2)3]I monolayer prepared from DMF showed greater stability among all the studied precursors. The X-ray photoelectron spectroscopy (XPS) analysis on a monolayer of [Mo3S7(S2CNMe2)3]I in THF assembled on Au/ITO suggested sulfur-rich composition with S:Mo ratio of 2.278. The Mo-S monolayer clusters resulting from [Mo3S7(S2CNMe2)3]I in THF showed a Tafel slope of 75.74 mV dec−1 and required a lower overpotential of 410 mV to reach a high HER catalytic current density of 100 mA cm−2 compared to the other studied precursors. Surface coverage of the Mo-S clusters on the Au surface was confirmed by cyclic voltammetry (CV) curves from K3Fe(CN)6 and anodization of Au surface. Further, the rotating ring-disk electrode (RRDE) measurements were performed for the monolayer of [Mo3S7(S2CNMe2)3]I prepared in THF to study its reaction kinetics. The HER catalytic activity of such monolayer Mo-S clusters can further be improved by controlling the sulfur vacancy. Full article
(This article belongs to the Special Issue Inorganic Materials for Solar Energy Conversion)
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14 pages, 11258 KiB  
Review
Bulky-Yet-Flexible Carbene Ligands and Their Use in Palladium Cross-Coupling
by Sofie M. P. Vanden Broeck, Fady Nahra and Catherine S. J. Cazin
Inorganics 2019, 7(6), 78; https://doi.org/10.3390/inorganics7060078 - 21 Jun 2019
Cited by 27 | Viewed by 5997
Abstract
In recent years, several classes of new N-heterocyclic carbene (NHC) ligands were developed around the concept of “flexible steric bulk”. The steric hindrance of these ligands brings stability to the active species, while ligand flexibility still allows for the approach of the [...] Read more.
In recent years, several classes of new N-heterocyclic carbene (NHC) ligands were developed around the concept of “flexible steric bulk”. The steric hindrance of these ligands brings stability to the active species, while ligand flexibility still allows for the approach of the substrate. In this review, the synthesis of several types of new classes, such as IBiox, cyclic alkyl amino carbenes (CAAC), ITent, and IPr* are discussed, as well as how they move the state-of-the-art in palladium catalyzed cross-coupling forward. Full article
(This article belongs to the Special Issue Palladium Catalysts: From Design to Applications)
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21 pages, 5538 KiB  
Article
Visible Light Sensitive SnO2/ZnCo2O4 Material for the Photocatalytic Removal of Organic Pollutants in Water
by Hadj Benhebal, Cédric Wolfs, Samir Kadi, Rémi G. Tilkin, Boualem Allouche, Radhwane Belabid, Valérie Collard, Alexandre Felten, Pierre Louette, Stéphanie D. Lambert and Julien G. Mahy
Inorganics 2019, 7(6), 77; https://doi.org/10.3390/inorganics7060077 - 21 Jun 2019
Cited by 18 | Viewed by 4247
Abstract
In this study, pure ZnCo2O4 and SnO2/ZnCo2O4 mix photocatalysts have been synthesized by the sol-gel process with three different SnO2 loading percentages (10, 20, and 30 wt %). Their photocatalytic activities were assessed on [...] Read more.
In this study, pure ZnCo2O4 and SnO2/ZnCo2O4 mix photocatalysts have been synthesized by the sol-gel process with three different SnO2 loading percentages (10, 20, and 30 wt %). Their photocatalytic activities were assessed on the degradation of organic pollutants in water under visible illumination. The structural, morphological, and optical properties were analyzed by X-ray diffraction (XRD), scanning electron microscopy, energy-dispersive X-ray (EDX), Fourier transform infrared (FTIR), nitrogen adsorption-desorption isotherms, X-ray photoelectron spectroscopy (XPS), and UV–Visible diffuse reflectance measurements. The results have shown that the materials are composed of a crystalline ZnCo2O4 matrix with a decrease in crystallite size with the amount of SnO2. Weakly crystalline SnO2 is also observed for loaded samples. The specific surface area is modified with the loading ratio. The evaluation of the photoactivity of the samples under visible light for the degradation of p-nitrophenol has highlighted that all materials are highly photoactive under visible light thanks to heterojunction between the two oxides. An application test has been conducted on a dye, congo red, showing the same tendencies. An optimal amount of SnO2 loading is observed for the sample containing 20 wt % of SnO2. A comparison with commercial Evonik P25 showed that the materials developed in this work have five to six times better efficiency under visible light, leading to a promising photocatalyst material. Full article
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11 pages, 4979 KiB  
Article
Molecular Modelling of the Ni(II)-Responsive Synechocystis PCC 6803 Transcriptional Regulator InrS in the Metal Bound Form
by Elia Barchi and Francesco Musiani
Inorganics 2019, 7(6), 76; https://doi.org/10.3390/inorganics7060076 - 21 Jun 2019
Cited by 6 | Viewed by 4088
Abstract
InrS (internal nickel-responsive sensor) is a transcriptional regulator found in cyanobacteria that represses the transcription of the nickel exporter NrsD in the apo form and de-represses expression of the exporter upon Ni(II) binding. Although a crystal structure of apo-InrS from Synechocystis PCC 6803 [...] Read more.
InrS (internal nickel-responsive sensor) is a transcriptional regulator found in cyanobacteria that represses the transcription of the nickel exporter NrsD in the apo form and de-represses expression of the exporter upon Ni(II) binding. Although a crystal structure of apo-InrS from Synechocystis PCC 6803 has been reported, no structure of the protein with metal ions bound is available. Here we report the results of a computational study aimed to reconstruct the metal binding site by taking advantage of recent X-ray absorption spectroscopy (XAS) data and to envisage the structural rearrangements occurring upon Ni(II) binding. The modelled Ni(II) binding site shows a square planar geometry consistent with experimental data. The structural details of the conformational changes occurring upon metal binding are also discussed in the framework of trying to rationalize the different affinity of the apo- and holo-forms of the protein for DNA. Full article
(This article belongs to the Special Issue Bioinorganic Chemistry of Nickel)
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19 pages, 3688 KiB  
Review
Iron Sulfide Materials: Catalysts for Electrochemical Hydrogen Evolution
by Dominikus Heift
Inorganics 2019, 7(6), 75; https://doi.org/10.3390/inorganics7060075 - 19 Jun 2019
Cited by 32 | Viewed by 7556
Abstract
The chemical challenge of economically splitting water into molecular hydrogen and oxygen requires continuous development of more efficient, less-toxic, and cheaper catalyst materials. This review article highlights the potential of iron sulfide-based nanomaterials as electrocatalysts for water-splitting and predominantly as catalysts for the [...] Read more.
The chemical challenge of economically splitting water into molecular hydrogen and oxygen requires continuous development of more efficient, less-toxic, and cheaper catalyst materials. This review article highlights the potential of iron sulfide-based nanomaterials as electrocatalysts for water-splitting and predominantly as catalysts for the hydrogen evolution reaction (HER). Besides new synthetic techniques leading to phase-pure iron sulfide nano objects and thin-films, the article reviews three new material classes: (a) FeS2-TiO2 hybrid structures; (b) iron sulfide-2D carbon support composites; and (c) metal-doped (e.g., cobalt and nickel) iron sulfide materials. In recent years, immense progress has been made in the development of these materials, which exhibit enormous potential as hydrogen evolution catalysts and may represent a genuine alternative to more traditional, noble metal-based catalysts. First developments in this comparably new research area are summarized in this article and discussed together with theoretical studies on hydrogen evolution reactions involving iron sulfide electrocatalysts. Full article
(This article belongs to the Special Issue Inorganic Materials for Solar Energy Conversion)
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15 pages, 4633 KiB  
Article
First Principles Study of the Vibrational and Thermal Properties of Sn-Based Type II Clathrates, CsxSn136 (0 ≤ x ≤ 24) and Rb24Ga24Sn112
by Hadeel Zahid, Dong Xue and Charles W. Myles
Inorganics 2019, 7(6), 74; https://doi.org/10.3390/inorganics7060074 - 14 Jun 2019
Cited by 1 | Viewed by 2573 | Correction
Abstract
After performing first-principles calculations of structural and vibrational properties of the semiconducting clathrates Rb24Ga24Sn112 along with binary CsxSn136 (0 ≤ x ≤ 24), we obtained equilibrium geometries and harmonic phonon modes. For the filled clathrate [...] Read more.
After performing first-principles calculations of structural and vibrational properties of the semiconducting clathrates Rb24Ga24Sn112 along with binary CsxSn136 (0 ≤ x ≤ 24), we obtained equilibrium geometries and harmonic phonon modes. For the filled clathrate Rb24Ga24Sn112, the phonon dispersion relation predicts an upshift of the low-lying rattling modes (~25 cm−1) for the Rb (“rattler”) compared to Cs vibration in CsxSn136. It is also found that the large isotropic atomic displacement parameter (Uiso) exists when Rb occupies the “over-sized” cage (28 atom cage) rather than the 20 atom counterpart. These guest modes are expected to contribute significantly to minimizing the lattice’s thermal conductivity (κL). Our calculation of the vibrational contribution to the specific heat and our evaluation on κL are quantitatively presented and discussed. Specifically, the heat capacity diagram regarding CV/T3 vs. T exhibits the Einstein-peak-like hump that is mainly attributable to the guest oscillator in a 28 atom cage, with a characteristic temperature 36.82 K for Rb24Ga24Sn112. Our calculated rattling modes are around 25 cm−1 for the Rb trapped in a 28 atom cage, and 65.4 cm−1 for the Rb encapsulated in a 20 atom cage. These results are utilized to predict the lattice’s thermal conductivity (approximately 0.62 W/m/K) in Rb24Ga24Sn112 within the kinetic theory approximation. Full article
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17 pages, 1006 KiB  
Article
Determination of pKa Values via ab initio Molecular Dynamics and its Application to Transition Metal-Based Water Oxidation Catalysts
by Mauro Schilling and Sandra Luber
Inorganics 2019, 7(6), 73; https://doi.org/10.3390/inorganics7060073 - 12 Jun 2019
Cited by 22 | Viewed by 5106
Abstract
The p K a values are important for the in-depth elucidation of catalytic processes, the computational determination of which has been challenging. The first simulation protocols employing ab initio molecular dynamics simulations to calculate p K a values appeared almost two decades ago. [...] Read more.
The p K a values are important for the in-depth elucidation of catalytic processes, the computational determination of which has been challenging. The first simulation protocols employing ab initio molecular dynamics simulations to calculate p K a values appeared almost two decades ago. Since then several slightly different methods have been proposed. We compare the performance of various evaluation methods in order to determine the most reliable protocol when it comes to simulate p K a values of transition metal-based complexes, such as the here investigated Ru-based water oxidation catalysts. The latter are of high interest for sustainable solar-light driven water splitting, and understanding of the underlying reaction mechanism is crucial for their further development. Full article
(This article belongs to the Special Issue Recent Advances in Water Oxidation Catalysis)
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13 pages, 2864 KiB  
Article
Photocracking Silica: Tuning the Plasmonic Photothermal Degradation of Mesoporous Silica Encapsulating Gold Nanoparticles for Cargo Release
by Jonas G. Croissant and Tania M. Guardado-Alvarez
Inorganics 2019, 7(6), 72; https://doi.org/10.3390/inorganics7060072 - 6 Jun 2019
Cited by 13 | Viewed by 4346
Abstract
The degradation of bionanomaterials is essential for medical applications of nanoformulations, but most inorganic-based delivery agents do not biodegrade at controllable rates. In this contribution, we describe the controllable plasmonic photocracking of gold@silica nanoparticles by tuning the power and wavelength of the laser [...] Read more.
The degradation of bionanomaterials is essential for medical applications of nanoformulations, but most inorganic-based delivery agents do not biodegrade at controllable rates. In this contribution, we describe the controllable plasmonic photocracking of gold@silica nanoparticles by tuning the power and wavelength of the laser irradiation, or by tuning the size of the encapsulated gold cores. Particles were literally broken to pieces or dissolved from the inside out upon laser excitation of the plasmonic cores. The photothermal cracking of silica, probably analogous to thermal fracturing in glass, was then harnessed to release cargo molecules from gold@silica@polycaprolactone nanovectors. This unique and controllable plasmonic photodegradation has implications for nanomedicine, photopatterning, and sensing applications. Full article
(This article belongs to the Special Issue Inorganic Nanoparticles in Cancer Therapy)
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11 pages, 735 KiB  
Article
σ-Holes vs. Buildups of Electronic Density on the Extensions of Bonds to Halogen Atoms
by Peter Politzer and Jane S. Murray
Inorganics 2019, 7(6), 71; https://doi.org/10.3390/inorganics7060071 - 6 Jun 2019
Cited by 3 | Viewed by 2696
Abstract
Our discussion focuses upon three possible features that a bonded halogen atom may exhibit on its outer side, on the extension of the bond. These are (1) a region of lower electronic density (a σ-hole) accompanied by a positive electrostatic potential with a [...] Read more.
Our discussion focuses upon three possible features that a bonded halogen atom may exhibit on its outer side, on the extension of the bond. These are (1) a region of lower electronic density (a σ-hole) accompanied by a positive electrostatic potential with a local maximum, (2) a region of lower electronic density (a σ-hole) accompanied by a negative electrostatic potential that also has a local maximum, and (3) a buildup of electronic density accompanied by a negative electrostatic potential that has a local minimum. In the last case, there is no σ-hole. We show that for diatomic halides and halogen-substituted hydrides, the signs and magnitudes of these maxima and minima can be expressed quite well in terms of the differences in the electronegativities of the halogen atoms and their bonding partners, and the polarizabilities of both. We suggest that the buildup of electronic density and absence of a σ-hole on the extension of the bond to the halogen may be an operational indication of ionicity. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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11 pages, 2061 KiB  
Article
Revealing the Nature of Chemical Bonding in an ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Telluride
by Kai C. Göbgen, Kai S. Fries, Fabian C. Gladisch, Richard Dronskowski and Simon Steinberg
Inorganics 2019, 7(6), 70; https://doi.org/10.3390/inorganics7060070 - 31 May 2019
Cited by 13 | Viewed by 3462
Abstract
Although the electronic structures of several tellurides have been recognized by applying the Zintl-Klemm concept, there are also tellurides whose electronic structures cannot be understood by applications of the aforementioned idea. To probe the appropriateness of the valence-electron transfers as implied [...] Read more.
Although the electronic structures of several tellurides have been recognized by applying the Zintl-Klemm concept, there are also tellurides whose electronic structures cannot be understood by applications of the aforementioned idea. To probe the appropriateness of the valence-electron transfers as implied by Zintl-Klemm treatments of ALn2Ag3Te5-type tellurides (A = alkaline-metal; Ln = lanthanide), the electronic structure and, furthermore, the bonding situation was prototypically explored for RbPr2Ag3Te5. The crystal structure of that type of telluride is discussed for the examples of RbLn2Ag3Te5 (Ln = Pr, Nd), and it is composed of tunnels which are assembled by the tellurium atoms and enclose the rubidium, lanthanide, and silver atoms, respectively. Even though a Zintl-Klemm treatment of RbPr2Ag3Te5 results in an (electron-precise) valence-electron distribution of (Rb+)(Pr3+)2(Ag+)3(Te2−)5, the bonding analysis based on quantum-chemical means indicates that a full electron transfer as suggested by the Zintl-Klemm approach should be considered with concern. Full article
(This article belongs to the Special Issue Structure, Properties, and Bonding in Solid State Compounds)
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26 pages, 4528 KiB  
Review
Recent Progress on Catalysts for the Positive Electrode of Aprotic Lithium-Oxygen Batteries †
by Yichao Cai, Yunpeng Hou, Yong Lu and Jun Chen
Inorganics 2019, 7(6), 69; https://doi.org/10.3390/inorganics7060069 - 28 May 2019
Cited by 8 | Viewed by 4276
Abstract
Rechargeable aprotic lithium-oxygen (Li-O2) batteries have attracted significant interest in recent years owing to their ultrahigh theoretical capacity, low cost, and environmental friendliness. However, the further development of Li-O2 batteries is hindered by some ineluctable issues, such as severe parasitic [...] Read more.
Rechargeable aprotic lithium-oxygen (Li-O2) batteries have attracted significant interest in recent years owing to their ultrahigh theoretical capacity, low cost, and environmental friendliness. However, the further development of Li-O2 batteries is hindered by some ineluctable issues, such as severe parasitic reactions, low energy efficiency, poor rate capability, short cycling life and potential safety hazards, which mainly stem from the high charging overpotential in the positive electrode side. Thus, it is of great significance to develop high-performance catalysts for the positive electrode in order to address these issues and to boost the commercialization of Li-O2 batteries. In this review, three main categories of catalyst for the positive electrode of Li-O2 batteries, including carbon materials, noble metals and their oxides, and transition metals and their oxides, are systematically summarized and discussed. We not only focus on the electrochemical performance of batteries, but also pay more attention to understanding the catalytic mechanism of these catalysts for the positive electrode. In closing, opportunities for the design of better catalysts for the positive electrode of high-performance Li-O2 batteries are discussed. Full article
(This article belongs to the Special Issue Electrochemical Energy Storage: Beyond Li-ion Technology)
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