Sustain. Chem., Volume 2, Issue 4 (December 2021) – 11 articles

Magic angle intensity decay and dynamic fluorescence anisotropy measurements were made on the binary solvent system composed of ethylammonium nitrate ([N_2,0,0,0⁺][NO₃⁻], EAN) + methanol (MeOH) across the complete EAN mole fraction range (x_IL = 0–1) using the neutral dipolar solute coumarin 153 (C153) at 295 K. Stokes–Einstein–Debye (SED) hydrodynamic theory was used as a model framework to assess the C153 rotational reorientation dynamics. Departure from stick SED prediction was observed (in contrast to literature reports that used cationic or anionic dyes) and indicated a significant influence of domain nanoheterogeneity on probe dynamics. Steady-state spectroscopy indicated minimal changes in spectral peak and width with mole fraction, except at x_IL = 0.3 where absorption widths decreased by ~170 cm⁻¹, signaling that C153 sensed a change in solution heterogeneity. Magic angle intensity decays corroborated the steady-state observation and the excited-state lifetimes showed a marked change from x_IL = 0.2–0.4 where EAN-EAN interactions became notably more significant. C153 average rotation times ($⟨{\tau }_{rot}⟩$) showed significant solvent decoupling with increased EAN. The rotational data were fit to a power law dependence, $⟨{\tau }_{rot}⟩\propto {\left(\frac{\eta }{T}\right)}^p$, where p = 0.82, demonstrating the presence of dynamic heterogeneity in the EAN/MeOH solutions. With increased EAN, rotation times showed that the heterogeneity became increasingly more significant since the rotation times systematically decreased away from the hydrodynamic stick limit. Full article

Chlorophylls and their derivatives have been extensively studied due to their unique and valuable properties, including their anti-mutagenic and anti-carcinogenic features. Nevertheless, high-purity-level chlorophylls extracted from natural sources are quite expensive because the methods used for their extraction have low selectivity and result in low yields. This study aimed to develop a “greener” and cost-effective technology for the extraction of chlorophylls from biomass using aqueous solutions of ionic liquids (ILs). Several aqueous solutions of ILs, with hydrotropic and surface-active effects were evaluated, demonstrating that aqueous solutions of surface-active ILs are enhanced solvents for the extraction of chlorophylls from spinach leaves. Operating conditions, such as the IL concentration and solid–liquid ratio, were optimized by a response surface methodology. Outstanding extraction yields (0.104 and 0.022 wt.% for chlorophyll a and b, respectively, obtained simultaneously) and selectivity (chlorophyll a/b ratio of 4.79) were obtained with aqueous solutions of hexadecylpyridinium chloride ([C₁₆py]Cl) at moderate conditions of temperature and time. These extraction yields are similar to those obtained with pure ethanol. However, the chlorophyll a/b ratio achieved with the IL aqueous solution is higher than with pure ethanol (3.92), reinforcing the higher selectivity afforded by IL aqueous solutions as viable replacements to volatile organic compounds and allowing the obtainment of more pure compounds. Finally, the recovery and reuse of the solvent were evaluated by using a back-extraction step of chlorophylls using ethyl acetate. The results disclosed here bring new perspectives into the design of new approaches for the selective extraction of chlorophylls from biomass using aqueous solutions of surface-active ILs. Full article

With the fast depleting rate of fossil fuels, the whole world is looking for promising energy sources for the future, and fuel cells are perceived as futuristic energy sources. Out of the different varieties of fuel cells, solid oxide fuel cells (SOFCs) are promising due to their unique multi-fuel operating capability without the need for an external reformer. Nonetheless, the state-of-the-art anode material Ni–YSZ undergoes carburization in presence of hydrocarbons (HCs), resulting in performance degradation. Several strategies have been explored by researchers to overcome the issue of carburization of the anode. The important strategies include reducing SOFC operating temperature, adjustment of steam: carbon ratio, and use of alternate anode catalysts. Among these, the use of alternate anodes is a promising strategy. Apart from the carburization issue, the anode can also undergo sulfur poisoning. The present review discusses carburization and sulfur poisoning issues and the different strategies that can be adopted for tackling them. The quintessence of this review is to provide greater insight into the various developments in hydrocarbon compatible anode catalysts and into the synthesis routes employed for the synthesis of hydrocarbon compatible anodes. Full article

The concept of mining or extracting valuable metals and minerals from technospheric stocks is referred to as technospheric mining. As potential secondary sources of valuable materials, mining these technospheric stocks can offer solutions to minimise the waste for final disposal and augment metals’ or minerals’ supply, and to abate environmental legacies brought by minerals’ extraction. Indeed, waste streams produced by the mining and mineral processing industry can cause long-term negative environmental legacies if not managed properly. There are thus strong incentives/drivers for the mining industry to recover and repurpose mine and mineral wastes since they contain valuable metals and materials that can generate different applications and new products. In this paper, technospheric mining of mine wastes and its application are reviewed, and the challenges that technospheric mining is facing as a newly suggested concept are presented. Unification of standards and policies on mine wastes and tailings as part of governance, along with the importance of research and development, data management, and effective communication between the industry and academia, are identified as necessary to progress technospheric mining to the next level. This review attempts to link technospheric mining to the promotion of environmental sustainability practices in the mining industry by incorporating green technology, sustainable chemistry, and eco-efficiency. We argue that developing environmentally friendly processes and green technology can ensure positive legacies from the mining industry. By presenting specific examples of the mine wastes, we show how the valuable metals or minerals they contain can be recovered using various metallurgical and mineral processing techniques to close the loop on waste in favour of a circular economy. Full article

This study focused on the use of citrus bio-waste and obtention of silica-based materials through the sol-gel technique for promoting a greener and more sustainable catalysis. The sol-gel method is a versatile synthesis route characterized by the low temperatures the materials are synthesized in, which allows the incorporation of organic components. This method is carried out by acid or alkali hydrolysis combined with bio-waste, such as orange and lemon peels, generated as co-products in the food processing industry. The main objective was to obtain silica-based materials from the precursor TEOS with different catalysts—acetic, citric and hydro-chloric acids and ammonium hydroxide—adding different percentages of lemon and orange peels in order to find the influence of bio-waste on acids/alkali precursor hydrolysis. This was to partially replace these catalysts for orange or lemon peels. The solids obtained were characterized with different techniques, such as SEM, FT₋IR, potentiometric titration and XRD. SEM images were compared with pure silica obtained to contrast the morphology of the acidic and alkali hydrolysis. However, until now, few attempts have been made to highlight the renewability of reagents used in the synthesis or to incorporate bio-based catalytic processes on larger scales. Full article

A systematic and structure-agnostic method for identifying heterogeneous activity of solid acids for catalyzing cellulose hydrolysis is presented. The basis of the method is preparation of a supernatant liquid by exposing the solid acid to reaction conditions and subsequent use of the supernatant liquid as a cellulose hydrolysis catalyst to determine the effects of in situ generated homogeneous acid species. The method was applied to representative solid acid catalysts, including polymer-based, carbonaceous, inorganic, and bifunctional materials. In all cases, supernatant liquids produced from these catalysts exhibited catalytic activity for cellulose hydrolysis. Direct comparison of the activity of the solid acid catalysts and their supernatants could not provide unambiguous detection of heterogeneous catalysis. A reaction pathway kinetic model was used to evaluate potential false-negative interpretation of the supernatant liquid test and to differentiate heterogeneous from homogeneous effects on cellulose hydrolysis. Lastly, differences in the supernatant liquids obtained in the presence and absence of cellulose were evaluated to understand possibility of false-positive interpretation, using structural evidence from the used catalysts to gain a fresh understanding of reactant–catalyst interactions. While many solid acid catalysts have been proposed for cellulose hydrolysis, to our knowledge, this is the first effort to attempt to differentiate the effects of heterogeneous and homogeneous activities. The resulting supernatant liquid method should be used in all future attempts to design and develop solid acids for cellulose hydrolysis. Full article

In the competitive market of plastic fillers, inexpensive and reliable materials are always sought after. Using a method of thermal conversion called pyrolysis, a potential contender was created from a plant biomass known as soybean hulls (SBH). SBH are a byproduct of the soybean farming industry and represent an abundant and inexpensive feedstock. The thermal conversion of SBH material gives rise to a lightweight carbon-rich filler called pyrolyzed soybean hulls (PSBH). We created two separate lots, lots A and B, with lot A corresponding to SBH pyrolyzed at 450 °C (PSBH-A) and lot B corresponding to SBH pyrolyzed at 500 °C (PSBH-B). Both lots of PSBH were also milled to reduce their particle size and tested against the as-received PSBH fillers. These milled materials were designated as ground soybean hulls (GSBH). Two different polyolefins, linear low-density polyethylene (LLDPE) and polypropylene (PP), were used for this study. The PSBH fillers were added to the polyolefins in weight percentages of 10%, 20%, 30%, 40%, and 50%, with the resulting plastic/PSBH composites being tested for their mechanical, thermal, and water absorption properties. In general, the addition of filler increased the maximum stress of the LLDPE/PSBH composites while reducing maximum stress of the PP/PSBH composites. The strain at maximum stress was reduced with increasing amounts of the PSBH filler for all composites. The modulus of elasticity generally increased with increasing filler amount. For thermal properties, the addition of the PSBH filler increased the heat distortion temperature, increased the thermal decomposition temperature, and reduced the heat of fusion of the composites compared to the neat polyolefins. The liquid absorption and thickness swelling in the materials were small overall but did increase with increasing amounts of the PSBH filler and with the time spent submerged in liquid. Milling the PSBH material into GSBH generally had small effects on the various tested material properties and led to easier mixing and a smoother finish on the surface of processed samples. The differences observed between lot A and lot B composites were often small or even negligible. Full article

Over 30 million ton of poly(ethylene terephthalate) (PET) is produced each year and no more than 60% of all PET bottles are reclaimed for recycling due to material property deteriorations during the mechanical recycling process. Herein, a sustainable approach is proposed to produce redox-active nanoparticles via the chemical upcycling of poly(ethylene terephthalate) (PET) waste for application in energy storage. Redox-active nanoparticles of sizes lower than 100 nm were prepared by emulsion polymerization of a methacrylic-terephthalate monomer obtained by a simple methacrylate functionalization of the depolymerization product of PET (i.e., bis-hydroxy(2-ethyl) terephthalate, BHET). The initial cyclic voltammetry results of the depolymerization product of PET used as a model compound show a reversible redox process, when using a 0.1 M tetrabutylammonium hexafluorophosphate/dimethyl sulfoxide electrolyte system, with a standard redox potential of −2.12 V vs. Fc/Fc⁺. Finally, the cycling performance of terephthalate nanoparticles was investigated using a 0.1 M TBAPF₆ solution in acetonitrile as electrolyte in a three-electrode cell. The terephthalate anode electrode displays good cycling stability and performance at high C-rate (i.e., ≥5C), delivering a stable specific discharge capacity of 32.8 mAh.g⁻¹ at a C-rate of 30 C, with a capacity retention of 94% after 100 cycles. However, a large hysteresis between the specific discharge and charge capacities and capacity fading are observed at lower C-rate (i.e., ≤2C), suggesting some irreversibility of redox reactions associated with the terephthalate moiety, in particular related to the oxidation process. Full article

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing. Full article

The extraction of valuable phytochemicals from natural sources is an important and constantly evolving research area. Zingiber officinale Roscoe (ginger) contains high amounts of bioactive phytochemicals, which are desirable due to their significant properties. In this work, the ability of different natural deep eutectic solvents (NaDESs) to serve as green solvents for the preparation of high added value extracts from ginger is explored, in combination with ultrasound assisted extraction. The method was optimized by applying a response surface methodology using the NaDES Bet/La/W (1:2:2.5). Three independent variables, namely the extraction time, ultrasound power and NaDES-to-dry-ginger ratio, were investigated by employing a 17-run three-level Box–Behnken Design (BBD) in order to study the correlation between the extraction conditions and the quality of the obtained extracts. The optimum conditions (in order to achieve simultaneously maximum total phenolic content and antioxidant activity), were found to be 23.8 min extraction time, 60 Watt and NaDES/ginger 25:1 w/w. In the optimum conditions the DPPH radical scavenging ability of the extracts was found to reach IC₅₀ = 18.16 mg/mL after 120 min, whereas the TPC was 20.10 ± 0.26 mg GAE/g of dry ginger. The green methodology was also compared with the extraction using conventional solvents. All the obtained extracts were evaluated for their antioxidant activity and their total phenolic content, while the extract derived by the optimum extraction conditions was further investigated for its ability to bind to calf thymus DNA (ctDNA). Full article

Herein, an ionic material (IM) with Förster Resonance Energy Transfer (FRET) characteristics is reported for the first time. The IM is designed by pairing a Nile Blue A cation (NBA⁺) with an anionic near-infrared (NIR) dye, IR820⁻, using a facile ion exchange reaction. These two dyes absorb at different wavelength regions. In addition, NBA⁺ fluorescence emission spectrum overlaps with IR820⁻ absorption spectrum, which is one requirement for the occurrence of the FRET phenomenon. Therefore, the photophysical properties of the IM were studied in detail to investigate the FRET mechanism in IM for potential dye sensitized solar cell (DSSCs) application. Detailed examination of photophysical properties of parent compounds, a mixture of the parent compounds, and the IM revealed that the IM exhibits FRET characteristics, but not the mixture of two dyes. The presence of spectator counterion in the mixture hindered the FRET mechanism while in the IM, both dyes are in close proximity as an ion pair, thus exhibiting FRET. All FRET parameters such as spectral overlap integral, Förster distance, and FRET energy confirm the FRET characteristics of the IM. This article presents a simple synthesis of a compound with FRET properties which can be further used for a variety of applications. Full article