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Chemistry, Volume 1, Issue 1 (December 2019) – 12 articles

Cover Story (view full-size image): Novel yolk@shell morphology has been successfully applied to produce Ni/ZnO@SiO2 and tested against benchmark systems such as Ni/CeO2 and Ni/Al2O3 in the DRM as a direct route for CO2 conversion. Although the Ni/ZnO@SiO2 material displayed middling performance compared to the reference materials, the morphology was found to successfully protect the active phase from sintering, while maintaining high levels of conversion for an extended duration that far surpassed the two reference materials. The yolk@shell material demonstrated impressive performance for over 180 hours and maintained a high H2/CO ratio throughout, showcasing the viability of this new nano-engineered catalyst for chemical CO2 recycling. View this paper.
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12 pages, 1090 KiB  
Article
Expanding the Scope of Asinger Chemistry towards Enantiomerically Pure Secondary Amines and β-Aminothiols through Chemoenzymatic Derivatization of 3-Thiazolines
by Mentor Hyseni, Nadine Zumbrägel, Heribert Offermanns and Harald Gröger
Chemistry 2019, 1(1), 180-191; https://doi.org/10.3390/chemistry1010012 - 28 Oct 2019
Viewed by 3533
Abstract
A proof of concept for a novel approach towards enantiomerically highly enriched acyclic secondary amines and β-aminothiols as non-cyclic target molecules when starting from 3-thiazolines as heterocycles is presented. Starting from 2,2,4,5,5-pentamethyl-3-thiazoline, we demonstrated this chemoenzymatic pathway to both of these types of [...] Read more.
A proof of concept for a novel approach towards enantiomerically highly enriched acyclic secondary amines and β-aminothiols as non-cyclic target molecules when starting from 3-thiazolines as heterocycles is presented. Starting from 2,2,4,5,5-pentamethyl-3-thiazoline, we demonstrated this chemoenzymatic pathway to both of these types of amine molecules, which were isolated as urea derivatives with a non-optimized yield of up to 20%. As a substrate, 2,2,4,5,5-pentamethyl-3-thiazolidine, which was obtained with an enantiomeric excess (ee) of 99% in a biotransformation from the corresponding 3-thiazoline according to a recently developed protocol, was used. For the reductive desulfurization of this substrate leading to a sulfur-free secondary amine, in situ formed Ni2B turned out to be a suitable reducing reagent. However, when using lithium aluminum hydride as a reducing agent, β-aminothiol was obtained. Full article
(This article belongs to the Section Molecular Organics)
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16 pages, 15295 KiB  
Article
Effect of Hydrazine Pretreatment on the Activity, Stability and Active Sites of Cobalt Species for Preferential Oxidation (PROX) of CO in H2-Rich Stream
by Reineck Mhlaba, Thuto Mosuang and Takalani Magadzu
Chemistry 2019, 1(1), 164-179; https://doi.org/10.3390/chemistry1010011 - 22 Oct 2019
Cited by 1 | Viewed by 3009
Abstract
The as-prepared (Co3O4) and hydrazine-treated (Co3O4(H)) cobalt catalysts were prepared using the precipitation method and evaluated at a temperature range of 40–220 °C for preferential oxidation (PROX) of CO in excess hydrogen. An improved surface [...] Read more.
The as-prepared (Co3O4) and hydrazine-treated (Co3O4(H)) cobalt catalysts were prepared using the precipitation method and evaluated at a temperature range of 40–220 °C for preferential oxidation (PROX) of CO in excess hydrogen. An improved surface reducibility with smaller crystallite size was noted on hydrazine-treated cobalt species (i.e., Co3O4(H) catalyst), which indicates some surface transformation. This finding correlates with the surface roughness formation (as depicted by scanning electron microscope (SEM) and transmission electron microscope (TEM) data), which was further confirmed by an increase in the Brunauer–Emmett–Teller (BET) surface area. The mesoporous structure of the Co3O4(H) catalyst remained intact, as compared to that of the Co3O4 catalyst. Interestingly, the in situ treatment of the standalone Co3O4(H) catalyst decreased the maximum CO conversion temperature (T100%) from 160 °C (over Co3O4) to 100 °C, with good selectivity. The Co3O4(H) catalyst showed good stability, with approximately 85% CO conversion at 100 °C for 21 h, as compared to a faster deactivation of the Co3O4 catalyst. However, the Co3O4(H) catalyst was unstable in both CO2 and the moisture environment. Based on the evaluation of spent hydrazine-treated (CoO(H)) cobalt catalyst, the high PROX activity is associated with the formation of Co3+ species as confirmed by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), and temperature-programmed reduction (TPR) data. Full article
(This article belongs to the Section Catalysis)
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38 pages, 4204 KiB  
Review
What’s in a Name?—A Short History of Coordination Chemistry from Then to Now
by Edwin C. Constable
Chemistry 2019, 1(1), 126-163; https://doi.org/10.3390/chemistry1010010 - 22 Aug 2019
Cited by 14 | Viewed by 10605
Abstract
This article traces the development of coordination chemistry and shows how progress in the science has been paralleled by the development of a vocabulary and nomenclature to describe new concepts, structural features and compound types. Full article
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15 pages, 3375 KiB  
Article
Solvatochromism and Selective Sorption of Volatile Organic Solvents in Pyridylbenzoate Metal-Organic Frameworks
by Christophe A. Ndamyabera, Savannah C. Zacharias, Clive L. Oliver and Susan A. Bourne
Chemistry 2019, 1(1), 111-125; https://doi.org/10.3390/chemistry1010009 - 15 Aug 2019
Cited by 4 | Viewed by 4879
Abstract
Using cobalt(II) as a metal centre with different solvent systems afforded the crystallization of isomorphous metal-organic frameworks {[Co(34pba)(44pba)]·DMF}n (1) and {[Co(34pba)(44pba)]·(C3H6O)}n (2) from mixed 4-(4-pyridyl)benzoate (44pba) and 3-(4-pyridyl)benzoate (34pba) ligands. Zinc(II) under the [...] Read more.
Using cobalt(II) as a metal centre with different solvent systems afforded the crystallization of isomorphous metal-organic frameworks {[Co(34pba)(44pba)]·DMF}n (1) and {[Co(34pba)(44pba)]·(C3H6O)}n (2) from mixed 4-(4-pyridyl)benzoate (44pba) and 3-(4-pyridyl)benzoate (34pba) ligands. Zinc(II) under the same reaction conditions that led to the formation of 1 formed an isostructural {[Zn(34pba)(44pba)]·DMF}n framework (3). Crystal structures of all three MOFs were elucidated and their thermal stabilities were determined. The frameworks of 1, 2, and 3 were activated under vacuum to form the desolvated forms 1d, 2d, and 3d, respectively. PXRD results showed that 1d and 2d were identical, consequently, 1d and 3d were then investigated for sorption of volatile organic compounds (VOCs) containing either chloro or amine moieties. Thermogravimetric analysis (TGA) and nuclear magnetic resonance (NMR) were used to determine the sorption capacity and selectivity for the VOCs. Some sorption products of 1d with amines became amorphous, but the crystalline framework could be recovered on desorption of the amines. Investigation of the sorption of water (H2O) and ammonia (NH3) in 1d gave rise to new phases identifiable by means of a colour change (solvatochromism). The kinetics of desorption of DMF, water and ammonia from frameworks 1d and 3d were studied using non-isothermal TGA. Activation energies for both cobalt(II) and zinc(II) frameworks are in the order NH3 < H2O < DMF, with values for the 1d analogue always higher than those for 3d. Full article
(This article belongs to the Special Issue Supramolecular Chemistry in the 3rd Millennium)
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22 pages, 6810 KiB  
Article
Effect of pH, Surfactant, and Temperature on Mixed-Phase Structure and Band Gap Properties of BiNbO4 Nanoparticles Prepared Using Different Routes
by Maram Bakiro, Salwa Hussein Ahmed and Ahmed Alzamly
Chemistry 2019, 1(1), 89-110; https://doi.org/10.3390/chemistry1010008 - 28 Jul 2019
Cited by 10 | Viewed by 4170
Abstract
α- and β-BiNbO4 nanoparticles were successfully prepared using three different routes, namely co-precipitation, hydrothermal, and citrate precursor methods. Structural characterization has been analyzed using powder X-ray diffraction where results confirmed the mixed-phase nature of the prepared powders. When co-precipitation method is applied, [...] Read more.
α- and β-BiNbO4 nanoparticles were successfully prepared using three different routes, namely co-precipitation, hydrothermal, and citrate precursor methods. Structural characterization has been analyzed using powder X-ray diffraction where results confirmed the mixed-phase nature of the prepared powders. When co-precipitation method is applied, BiNbO4 prepared at pH 2 and calcined at 750 °C shows predominately the α-BiNbO4 owning the narrowest band gap of 2.86 eV, whereas an increase in the pH value resulted in the β-BiNbO4 phase being the predominant phase. On the other hand, samples prepared using citrate precursor method show co-existence of both α- and β-BiNbO4 at all pH values under study; however, at pH 10 the β-BiNbO4 was the dominant phase exhibiting a higher bandgap energy value of 3.16 eV. When applying the hydrothermal approach, BiNbO4 prepared at all pH ranges of the present study show a band gap >3.2 eV indicating their activity in the ultraviolet region of the spectrum. Moreover, increasing calcination temperature to 900 °C, a gradual transformation of α- to β was observed. Lastly, it was noticed that as the lattice volume increases, the band gap of prepared BiNbO4 decreases. Full article
(This article belongs to the Section Chemistry at the Nanoscale)
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9 pages, 1459 KiB  
Communication
Hydroquinone-Based Anion Receptors for Redox-Switchable Chloride Binding
by Daniel A. McNaughton, Xiaochen Fu, William Lewis, Deanna M. D’Alessandro and Philip A. Gale
Chemistry 2019, 1(1), 80-88; https://doi.org/10.3390/chemistry1010007 - 11 Jul 2019
Cited by 6 | Viewed by 5034
Abstract
A series of chloride receptors has been synthesized containing an amide hydrogen bonding site and a hydroquinone motif. It was anticipated that oxidation of the hydroquinone unit to quinone would greatly the diminish chloride binding affinity of these receptors. A conformational switch is [...] Read more.
A series of chloride receptors has been synthesized containing an amide hydrogen bonding site and a hydroquinone motif. It was anticipated that oxidation of the hydroquinone unit to quinone would greatly the diminish chloride binding affinity of these receptors. A conformational switch is promoted in the quinone form through the formation of an intramolecular hydrogen bond between the amide and the quinone carbonyl, which blocks the amide binding site. The reversibility of this oxidation process highlighted the potential of these systems for use as redox-switchable receptors. 1H-NMR binding studies confirmed stronger binding capabilities of the hydroquinone form compared to the quinone; however, X-ray crystal structures of the free hydroquinone receptors revealed the presence of an analogous inhibiting intramolecular hydrogen bond in this state of the receptor. Binding studies also revealed interesting and contrasting trends in chloride affinity when comparing the two switch states, which is dictated by a secondary interaction in the binding mode between the amide carbonyl and the hydroquinone/quinone couple. Additionally, the electrochemical properties of the systems have been explored using cyclic voltammetry and it was observed that the reduction potential of the system was directly related to the expected strength of the internal hydrogen bond. Full article
(This article belongs to the Special Issue Supramolecular Chemistry in the 3rd Millennium)
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11 pages, 9039 KiB  
Article
Acetylation of Alcohols, Amines, Phenols, Thiols under Catalyst and Solvent-Free Conditions
by Nagaraj Anbu, Nagarathinam Nagarjun, Manju Jacob, J. Mary Vimala Kumari Kalaiarasi and Amarajothi Dhakshinamoorthy
Chemistry 2019, 1(1), 69-79; https://doi.org/10.3390/chemistry1010006 - 10 Jul 2019
Cited by 25 | Viewed by 25978
Abstract
In the present study, an easy and an efficient approach is reported for the acetylation of alcohols, amines, phenols, and thiols under solvent- and catalyst-free conditions. The experimental conditions were milder than conventional methods and the reactions were completed in shorter reaction time. [...] Read more.
In the present study, an easy and an efficient approach is reported for the acetylation of alcohols, amines, phenols, and thiols under solvent- and catalyst-free conditions. The experimental conditions were milder than conventional methods and the reactions were completed in shorter reaction time. The examined substrates afforded higher yields of the acetylated products under the short reaction time. Comparison of this work with earlier reported procedures reveals that this method offers some advantages than with reported catalysts and solvents. The as-synthesized products were characterized by 1H-NMR and GC-MS techniques to ensure their purity and identity. In addition, a possible mechanism was also proposed for this reaction. Full article
(This article belongs to the Section Catalysis)
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25 pages, 9884 KiB  
Review
Solid-State Electrochemical Process and Performance Optimization of Memristive Materials and Devices
by Wuhong Xue, Xiao-Hong Xu and Gang Liu
Chemistry 2019, 1(1), 44-68; https://doi.org/10.3390/chemistry1010005 - 21 Mar 2019
Cited by 4 | Viewed by 5990
Abstract
As an emerging technology, memristors are nanoionic-based electrochemical systems that retains their resistance state based on the history of the applied voltage/current. They can be used for on-chip memory and storage, biologically inspired computing, and in-memory computing. However, the underlying physicochemical processes of [...] Read more.
As an emerging technology, memristors are nanoionic-based electrochemical systems that retains their resistance state based on the history of the applied voltage/current. They can be used for on-chip memory and storage, biologically inspired computing, and in-memory computing. However, the underlying physicochemical processes of memristors still need deeper understanding for the optimization of the device properties to meet the practical application requirements. Herein, we review recent progress in understanding the memristive mechanisms and influential factors for the optimization of memristive switching performances. We first describe the working mechanisms of memristors, including the dynamic processes of active metal ions, native oxygen ions and other active ions in ECM cells, VCM devices and ion gel-based devices, and the switching mechanisms in organic devices, along with discussions on the influential factors of the device performances. The optimization of device properties by electrode/interface engineering, types/configurations of dielectric materials and bias scheme is then illustrated. Finally, we discuss the current challenges and the future development of the memristor. Full article
(This article belongs to the Section Electrochemistry and Photoredox Processes)
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27 pages, 10252 KiB  
Review
Recent Progress in Two-Dimensional Nanomaterials for Laser Protection
by Zhiwei Liu, Bin Zhang and Yu Chen
Chemistry 2019, 1(1), 17-43; https://doi.org/10.3390/chemistry1010004 - 16 Jan 2019
Cited by 25 | Viewed by 6584
Abstract
The Nobel Prize in Physics 2018, “For groundbreaking inventions in the field of laser physics”, went to Arthur Ashkin and Gérard Mourou and Donna Strickland. Their inventions have revolutionized laser physics and greatly promoted the development of laser instruments, which have penetrated into [...] Read more.
The Nobel Prize in Physics 2018, “For groundbreaking inventions in the field of laser physics”, went to Arthur Ashkin and Gérard Mourou and Donna Strickland. Their inventions have revolutionized laser physics and greatly promoted the development of laser instruments, which have penetrated into many aspects of people’s daily lives. However, for the purpose of protecting human eyes or optical instruments from being damaged by both pulsed and continuous wave laser radiation, the research on laser protective materials is of particular significance. Due to the intriguing and outstanding physical, chemical, and structural properties, two-dimensional (2D) nanomaterials have been extensively studied as optical limiting (OL) materials owing to their broadband nonlinear optical (NLO) response and fast carrier relaxation dynamics that are important for reducing the laser intensity. This review systematically describes the OL mechanisms and the recent progress in 2D nanomaterials for laser protection. Full article
(This article belongs to the Section Chemistry at the Nanoscale)
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14 pages, 2119 KiB  
Article
Advantages of Yolk Shell Catalysts for the DRM: A Comparison of Ni/ZnO@SiO2 vs. Ni/CeO2 and Ni/Al2O3
by Cameron Alexander Hurd Price, Emily Earles, Laura Pastor-Pérez, Jian Liu and Tomas Ramirez Reina
Chemistry 2019, 1(1), 3-16; https://doi.org/10.3390/chemistry1010003 - 28 Dec 2018
Cited by 21 | Viewed by 6465
Abstract
Encapsulation of metal nanoparticles is a leading technique used to inhibit the main deactivation mechanisms in dry reforming of methane reaction (DRM): Carbon formation and Sintering. Ni catalysts (15%) supported on alumina (Al2O3) and ceria (CeO2) have [...] Read more.
Encapsulation of metal nanoparticles is a leading technique used to inhibit the main deactivation mechanisms in dry reforming of methane reaction (DRM): Carbon formation and Sintering. Ni catalysts (15%) supported on alumina (Al2O3) and ceria (CeO2) have shown they are no exception to this analysis. The alumina supported catalysts experienced graphitic carbonaceous deposits, whilst the ceria showed considerable sintering over 15 h of DRM reaction. The effect of encapsulation compared to that of the performance of uncoated catalysts for DRM reaction has been examined at different temperatures, before conducting longer stability tests. The encapsulation of Ni/ZnO cores in silica (SiO2) leads to advantageous conversion of both CO2 and CH4 at high temperatures compared to its uncoated alternatives. This work showcases the significance of the encapsulation process and its overall effects on the catalytic performance in chemical CO2 recycling via DRM. Full article
(This article belongs to the Special Issue CO2, a Carbon Source for Chemicals and Fuels)
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1 pages, 146 KiB  
Editorial
Welcome to Chemistry—An International Open Access Journal
by Edwin C. Constable
Chemistry 2019, 1(1), 2; https://doi.org/10.3390/chemistry1010002 - 18 Dec 2018
Viewed by 3465
Abstract
It is a great pleasure to welcome you to Chemistry—An International Journal. [...] Full article
1 pages, 158 KiB  
Editorial
Publisher's Notice: Chemistry—An International Journal
by Shu-Kun Lin
Chemistry 2019, 1(1), 1; https://doi.org/10.3390/chemistry1010001 - 18 Dec 2018
Cited by 7 | Viewed by 3339
Abstract
MDPI is launching Chemistry—An International Journal [...] Full article
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