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Sustain. Chem., Volume 3, Issue 4 (December 2022) – 8 articles

Cover Story (view full-size image): Organobromides represent a significantly important product class that are mainly produced via traditional bromination methods utilizing highly volatile and corrosive bromine or its surrogates in the presence of excess oxidizers. Electrochemical bromination and bromofunctionalization provide a sustainable and green alternative to the conventional synthetic protocols via generating bromine in situ under controlled conditions from bench-stable bromide salts and electricity as sole oxidizing reagents. The superiority of synthetic electrochemistry is demonstrated via a collection of diverse and widely established electrochemical bromofunctionalization protocols to form synthetically important commodities based on alkenes and alkynes. View this paper
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7 pages, 1871 KiB  
Communication
Electrochemical Synthesis of 1,1′-Binaphthalene-2,2′-Diamines via Transition-Metal-Free Oxidative Homocoupling
by Duona Fan, Md. Imrul Khalid, Ganesh Tatya Kamble, Hiroaki Sasai and Shinobu Takizawa
Sustain. Chem. 2022, 3(4), 551-557; https://doi.org/10.3390/suschem3040034 - 04 Dec 2022
Cited by 1 | Viewed by 2278
Abstract
The facile and green synthesis of 1,1′-binaphthalene-2,2′-diamine (BINAM) derivatives was established via the anodic dehydrogenative homo-coupling of 2-naphthylamines. The sustainable protocol provided a series of BINAMs in excellent yields of up to 98% with good current efficiency (66%) and H2 as the [...] Read more.
The facile and green synthesis of 1,1′-binaphthalene-2,2′-diamine (BINAM) derivatives was established via the anodic dehydrogenative homo-coupling of 2-naphthylamines. The sustainable protocol provided a series of BINAMs in excellent yields of up to 98% with good current efficiency (66%) and H2 as the sole coproduct without utilizing transition-metal reagents or stoichiometric oxidants. Full article
(This article belongs to the Topic Green and Sustainable Chemistry)
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16 pages, 1282 KiB  
Article
Removal of Metals by Biomass Derived Adsorbent in Its Granular and Powdered Forms: Adsorption Capacity and Kinetics Analysis
by Ana Beatriz Soares Aguiar, Josiel Martins Costa, Gabriela Espirito Santos, Giselle Patrícia Sancinetti and Renata Piacentini Rodriguez
Sustain. Chem. 2022, 3(4), 535-550; https://doi.org/10.3390/suschem3040033 - 02 Dec 2022
Cited by 2 | Viewed by 1491
Abstract
Among the various existing metals, zinc and copper are predominant metals in several effluents from industries such as electroplating, plastics production and mining. Technical methods have been applied in the treatment of effluents containing metals, including chemical removal, adsorption, ion exchange, membrane technologies [...] Read more.
Among the various existing metals, zinc and copper are predominant metals in several effluents from industries such as electroplating, plastics production and mining. Technical methods have been applied in the treatment of effluents containing metals, including chemical removal, adsorption, ion exchange, membrane technologies and electrochemistry. However, it is necessary to develop technologies that minimize costs and increase treatment quality while reducing residual sludge generation. Adsorption using biological materials stands out for removing metals, a low-cost technique and high efficiency. Thus, this study evaluated metal adsorption using an adsorbent from granular and powdered anaerobic sludge, followed by a kinetic analysis, aiming at a new alternative for wastewater treatment. Evaluation of the copper and zinc adsorption process using granular and powdered biomass resulted in maximum removals of 72.9% and 62.7% for zinc, respectively, and 92.8% and 85.0% for copper, respectively. Analyzing the kinetic models, the pseudo-second-order model fitted the data better. Applying the kinetics of other studies in the literature for copper and zinc removal by other adsorbents, the pseudo-second-order model was the most representative model. In this context, kinetic modeling allowed the determination of the solute removal rate, estimating the adsorption mechanism. Full article
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15 pages, 2465 KiB  
Article
The Role of Pozzolanic Activity of Siliceous Fly Ash in the Formation of the Structure of Sustainable Cementitious Composites
by Grzegorz Ludwik Golewski
Sustain. Chem. 2022, 3(4), 520-534; https://doi.org/10.3390/suschem3040032 - 01 Dec 2022
Cited by 30 | Viewed by 2171
Abstract
The following article introduces, in a thorough manner, how the chemical pozzolanic reaction takes place in cement composites containing the fly ash (FA) additive. In the research part, however, the development of phases in the structure of the cement paste in the initial [...] Read more.
The following article introduces, in a thorough manner, how the chemical pozzolanic reaction takes place in cement composites containing the fly ash (FA) additive. In the research part, however, the development of phases in the structure of the cement paste in the initial period of its curing and after 28 days from its preparation was traced. For this purpose, a Scanning Electron Microscope (SEM) was used. In order to accurately highlight all the characteristic stages of the formation of the structure of the composite containing FA, an analysis of the cement matrix was carried out between 0.5 and 28 days of their curing. Microstructural studies were complemented by tests of pozzolanic activity of FAs used. In order to conduct a full analysis of this feature, experiments were carried out using two types of research methods, i.e., chemical and physical. On the basis on the conducted studies it was found that: in cement composites with the addition of FA, in the period until the third day of curing, the development of the material structure is mainly the result of the hydration reaction, and between the seventh and fourteenth day after sample preparation, the first signs of the pozzolanic reaction on FA grains are visible; however, in the period between 14 and 28 days, there is a clear homogenization of the structure of the cement composite with the addition of FA, resulting from the change of disordered phases into compact and homogeneous forms and filling in the composite of porous places with pozzolanic reaction products. The use of cement composites based on materials whose application makes it possible to reduce GHG emissions to the atmosphere, reduce energy consumption, and reduce industrial waste landfills leads towards the development of ecological and sustainable building engineering. Full article
(This article belongs to the Topic Green and Sustainable Chemistry)
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9 pages, 558 KiB  
Article
Revisiting the Absorption Spectra of Polycyclic Aromatic Hydrocarbons over Porto (Portugal) by TD-DFT Calculations
by Guilherme M. Fernandes, Francisco J. D. Macedo, Joaquim C. G. Esteves da Silva and Luís Pinto da Silva
Sustain. Chem. 2022, 3(4), 511-519; https://doi.org/10.3390/suschem3040031 - 30 Nov 2022
Viewed by 1684
Abstract
Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have [...] Read more.
Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the “real-world” absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds. Full article
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29 pages, 9336 KiB  
Article
Sustainable Grinding Performances of Nano-Sic Reinforced Al Matrix Composites under MQL: An Integrated Box–Behnken Design Coupled with Artificial Bee Colony (ABC) Algorithm
by A. Nandakumar, T. Rajmohan, S. Vijayabhaskar and D. Vijayan
Sustain. Chem. 2022, 3(4), 482-510; https://doi.org/10.3390/suschem3040030 - 14 Nov 2022
Cited by 2 | Viewed by 1109
Abstract
The presence of abrasive particles in ceramic reinforced composite materials makes the machining complicated by generating friction at elevated temperatures. Lubricants can be used to prohibit the hazard of higher temperatures. This research work is focused on examining the effects of lubricants on [...] Read more.
The presence of abrasive particles in ceramic reinforced composite materials makes the machining complicated by generating friction at elevated temperatures. Lubricants can be used to prohibit the hazard of higher temperatures. This research work is focused on examining the effects of lubricants on the grinding performances of Al matrix composites reinforced with nano-SiC particles under minimum quantity lubrication (MQL). A cylindrical grinding machine is used to perform the grinding experiments by employing a Box–Behnken design. Multiple performances, such as surface roughness, grinding forces and temperature, are optimized by considering the depth of cut, speed of the workpiece, wheel speed and wt % of nano-SiC using response surface methodology (RSM)-based artificial bee colony (ABC) algorithm. Atomic force microscope (AFM) and scanning electron microscopy (SEM) are used to observe the morphologies of the machined surfaces and the wheel. Full article
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7 pages, 375 KiB  
Brief Report
Metal and Molecular Vapor Separation Analysis for Direct Determination of Mn and Cu by Atomic Absorption Detection, Free of Background Absorption
by Ikki Tateishi, Mai Furukawa, Hideyuki Katsumata and Satoshi Kaneco
Sustain. Chem. 2022, 3(4), 475-481; https://doi.org/10.3390/suschem3040029 - 02 Nov 2022
Cited by 2 | Viewed by 1219
Abstract
The metal and molecular vapor separation analysis (MMVSA) of solid samples with an atomic absorption detector (AA) was investigated for the direct determination of manganese and copper in biological materials. An open column made with a molybdenum tube (i.d. 1.22 mm) with three-ring [...] Read more.
The metal and molecular vapor separation analysis (MMVSA) of solid samples with an atomic absorption detector (AA) was investigated for the direct determination of manganese and copper in biological materials. An open column made with a molybdenum tube (i.d. 1.22 mm) with three-ring supporters was developed. Pure argon as a carrier gas flowed at a flow rate of 4.0 mL min−1. An ultrasonic agitation method was used for suspending NIST standard reference material powders in water. Manganese and copper in the biological powders were completely separated from Al, Ca, Fe, K, Mg, Na, and Zn elements by MMVSA under optimal experimental conditions. Several NIST biological samples were directly analyzed with satisfactory results. It was found that manganese and copper in biological materials without interferences from matrix elements could be directly determined after only an ultrasonic agitation of the biological powders. The advantages of the slurry sampling of MMVSA are simplicity, low cost, a high speed of analysis, and rapid calibration. Full article
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20 pages, 4749 KiB  
Article
Poly (Vinylidene Difluoride) Polymer in 1-Ethyl-3-methylimidazolium Acetate and Acetic Acid Containing Solvents: Tunable and Recoverable Solvent Media to Induce Crystalline Phase Transition and Porosity
by Santosh Govind Khokarale, Piotr Jablonski, Dariush Nikjoo, Van Minh Dinh, Ola Sundman, Knut Irgum and Jyri-Pekka Mikkola
Sustain. Chem. 2022, 3(4), 455-474; https://doi.org/10.3390/suschem3040028 - 29 Oct 2022
Viewed by 1409
Abstract
In this report, 1-ethyl-3-methylimidazolium acetate, [EMIM][AcO] ionic liquid (IL) and acetic acid (AA) comprised solvents were used for the thermal treatment of poly (vinylidene difluoride), PVDF. Here, besides the various combinations of IL and AA in solvents, the pure IL and AA were [...] Read more.
In this report, 1-ethyl-3-methylimidazolium acetate, [EMIM][AcO] ionic liquid (IL) and acetic acid (AA) comprised solvents were used for the thermal treatment of poly (vinylidene difluoride), PVDF. Here, besides the various combinations of IL and AA in solvents, the pure IL and AA were also applied as a solvent upon thermal treatments. The samples obtained after the treatment were analysed for structural and crystalline phase changes, porosity, and molecular weight distribution with various analytical techniques. The Kamlet-Taft parameters measurement of the IL and AA containing solvents with different solvatochromic dyes was also performed to examine their solvent properties and correlate with the properties of the treated PVDF materials. The treatment of PVDF with pure IL results in the formation of highly carbonaceous material due to extensive dehydroflurination (DHF) as well as possibly successive cross-linking in the polymer chains. Upon IL and AA combined solvent treatment, the neat PVDF which composed of both α- and β crystalline phases was transformed to porous and β-phase rich material whereas in case of pure AA the non-porous and pure α-phase polymeric entity was obtained. A combined mixture of IL and AA resulted in a limited the DHF process and subsequent cross-linking in the polymer chains of PVDF allowed the formation of a porous material. It was observed that the porosity of the thermally treated materials was steadily decreasing with increase in the amount of AA in solvents composition and solvent with an AA:IL mole ratio of 2:1 resulted in a PVDF material with the highest porosity amongst the applied solvents. A recovery method for the IL and AA combined solvent after the thermal treatment of PVDF was also established. Hence, with varying the type of solvents in terms of composition, the highly carbonaceous materials as well as materials with different porosities as well as crystalline phases can be obtained. Most importantly here, we introduced new IL and AA containing recoverable solvents for the synthesis of porous PVDF material with the electroactive β-phase. Full article
(This article belongs to the Special Issue Alternative Solvents for Green Chemistry)
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25 pages, 4572 KiB  
Review
Electrochemical Bromofunctionalization of Alkenes and Alkynes—To Sustainability and Beyond
by Lilla G. Gombos and Siegfried R. Waldvogel
Sustain. Chem. 2022, 3(4), 430-454; https://doi.org/10.3390/suschem3040027 - 13 Oct 2022
Cited by 10 | Viewed by 2541
Abstract
The electrochemical generation of highly reactive and hazardous bromine under controlled conditions as well as the reduction of surplus oxidizers and reagent waste has placed electrochemical synthesis in a highlighted position. In particular, the electrochemical dibromination and bromofunctionalization of alkenes and alkynes have [...] Read more.
The electrochemical generation of highly reactive and hazardous bromine under controlled conditions as well as the reduction of surplus oxidizers and reagent waste has placed electrochemical synthesis in a highlighted position. In particular, the electrochemical dibromination and bromofunctionalization of alkenes and alkynes have received significant attention, as the forming of synthetically important derivatives can be generated from bench-stable and safe bromide sources under “green” conditions. Readily available and non-corrosive bromide salts have been utilized with a dual role as both a reagent and supporting electrolyte. However, this trend seems to change with the preparation of organobromine species. In this review, the electrochemical dibromination and bromofunctionalization of alkenes and alkynes was addressed in terms of their bromine sources and sustainability. Full article
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