The Tetrahedron approach is a new environmental tool adapted to assess the sustainability of anthropogenic processes. This tool is based on a four-step methodology that includes (a) the identification of critical parameters, (b) evaluation through the Tetrahedron Parameter Global Evaluator, (c) construction of a tetrahedron diagram based on the final scores and (d) quantitative estimation of the global sustainability. The Tetrahedron incorporates various aspects of sustainability, including economic, social and environmental factors, and provides a comprehensive framework for evaluating the impact of human activities. This article presents the methodology and application of the Tetrahedron in determining the sustainability of five case studies: CO2 capture, unconventional methanol production, the Solvay process, CO2-alcoholic fermentation process strategy and the CO2-Rumen fermentation process strategy. The results demonstrate the Tetrahedron as an effective and reliable tool to quantify the sustainability of anthropogenic processes and to promote sustainable practices across various industries and sectors. The Tetrahedron offers several advantages over other environmental assessment tools, including holistic approach, simplicity and flexibility.

How to retrieve and reuse surfactants efficiently from surfactant-based microemulsions (MEs) has long been a problem, which is full of challenges and needs to be solved urgently. To this end, a pH-triggered precipitation-dissolution (PTPD) strategy is developed. The surfactant sodium 3-(laurylamino)propane-1-sulfonate (LMPS) transforms into an insoluble precipitate (the inner salt of LMPS, LMP) after reaction with HCl, by which the monophasic LMPS-based MEs demulsified entirely, giving a separable mixture of oil, water and LMP. LMP can be retrieved efficiently (~95.3%) regardless of the ME type, and can then be conveniently restored to LMPS via reactions with NaOH. Conceptually, the retrieval of LMPS (~96.6%), toxic benzo[a]pyrene (BaP, ~99.5%) and a mixture of co-surfactant n-butanol and the oil phase n-heptane (~97.1%) from the sufficiently emulsified soil eluents is achievable by respectively using the PTPD strategy and distillation, wherein the soil eluents were generated from the remediation of BaP-contaminated soil using an oil-in-water LMPS-based ME as washing agent. It reveals a promising future for the PTPD strategy in the post-processing of soil eluents containing toxic hydrophobic organic contaminants and excessive surfactants.

We present an innovative process for directly transforming poly(ethylene terephthalate) (PET), a polymer extensively used in food and beverage packaging, into trans-isomer-enriched 1,4-cyclohexanedimethanol (CHDM), a key ingredient in advanced specialty polymers. Our approach leverages a dual-catalyst system featuring palladium on reduced graphene oxide (Pd/r-GO) and oxalate-gel-derived copper-zinc oxide (og-CuZn), utilizing hydrogenation/hydrogenolysis relay catalysis. This method efficiently transforms PET into polyethylene-1,4-cyclohexanedicarboxylate (PECHD), which is then converted into CHDM with an impressive overall yield of 95 % in a two-stage process. Our process effectively handles various post-consumer PET plastics, converting them into CHDM with yields between 78 % and 89 % across different substrates. Additionally, we demonstrate the applicability and scalability of this approach through a temperature-programmed three-stage relay process on a 10-gram scale, which results in purified CHDM with an isolated yield of 87 % and a notably higher trans/cis ratio of up to 4.09/1, far exceeding that of commercially available CHDM. This research not only provides a viable route for repurposing PET waste but also enhances the control of selectivity patterns in multistage relay catalysis.

Driven by escalating environmental concerns, synthetic chemistry faces an urgent need for a green revolution. Green chemistry, with its focus on low environmental impacting chemicals and minimized waste production, emerges as a powerful tool in addressing this challenge. Metrics such as the E-factor guide the design of environmentally friendly strategies for chemical processes by quantifying the waste generated in obtaining target products, thus enabling interventions to minimize it. Phthalocyanines (Pcs), versatile molecules with exceptional physical and chemical properties, hold immense potential for technological applications. This review aims to bridge the gap between green chemistry and phthalocyanine synthesis by collecting the main examples of environmentally sustainable syntheses documented in the literature. The calculation of the E-factor of a selection of them provides insights on how crucial it is to evaluate a synthetic process in its entirety. This approach allows for a better evaluation of the actual sustainability of the phthalocyanine synthetic process and indicates possible strategies to improve it.

The valorization of humins side streams from bio-refineries holds significant economic and sustainability potential. One plausible strategy involves using them as building blocks to create new materials. However, humins pose conceptual challenges in their natural state due to their high viscosity, processing difficulties, and temperature sensitivity. This article presents a synthetic strategy for modifying humins properties to make them thermally stable and processable. Employing a sequence of esterification reactions and varying the reagent steric length, we showcase the selective transformation of humins into thermally-stable fine powders and low-viscosity liquids. We extend this approach by reacting humins with polyesters such as polylactic acids and polycaprolactone. In particular, we detail a one-pot single-step synthesis of micro-phase separated compatibilized blends of polylactic acid and humins capped with the polylactic acid arms. Processed via solution-casting, the obtained materials behave as high-strength thermoplastic elastomers having uniform foam morphologies and material characteristics superior to the pure polylactic acid. By varying the content of D-enantiomers, we demonstrate an additional possibility of manipulating the cellular structures of the foams. Finally, we provide a solution to product circularity by reporting a dissolution recycling method.

OBJECTIVE: The establishment of a green and sustainable Knoevenagel condensation reaction in organic chemistry is still crucial. This work aimed to provide a newly developed metal-free and halogen-free catalytic methodology for the synthesis of CS and (hetero-) arylidene malononitriles in the laboratory and industrial scale. The Knoevenagel condensation reaction of various carbonyl groups with malononitrile was investigated in ethanol, an ecofriendly medium, in the presence of seven nitrogen-based organocatalysts.
METHODS: A comparative study was conducted using two as-obtained and four commercially available nitrogen-based organocatalysts in Knoevenagel condensation reactions. The synthesis of CS gas (2-chlorobenzylidene malononitrile) using a closed catalytic system was optimized based on their efficiency and greener approach.
RESULTS: The conversion of 100% and excellent yields were obtained in a short time. The products could be crystallized directly from the reaction mixture. After separating pure products, the residue solution was employed directly in the next run without any concentration, activation, purification, or separation. Furthermore, the synthesis of 2-chlorobenzylidenemahmonitrile (CS) was carried out on a large scale using imidazole as a selected nitrogen-based catalyst, afforded crystalline products with 95 ± 2% yield in five consecutive runs.
CONCLUSIONS: Energy efficiency, cost saving, greener conditions, using only 5 mol% of organocatalyst, high recyclability of catalyst, prevention of waste, recycling extractant by a rotary evaporator for non-crystallized products, demonstrated the potential commercial production of CS using imidazole in ethanol as an efficient and highly recyclable catalytic system.

Block copolymers utilizing oligomeric poly(pentylene-co-hexylene carbonate)diol modified with 2,4-diisocyanatotoluene and further with 2-bromo-N-(3-hydroxypropyl)-2-methylpropanamide were synthesized and utilized as Activators ReGenerated by Electron Transfer Atom Transfer Radical Polymerization macroinitiators to obtain a first generation of multifunctional recycling additives with poly(glycidyl methacrylate-co-butyl methacrylate-co-methyl methacrylate) side chains, which could act as chain extenders. Then, chosen additive was reacted with a radical scavenger, 3,5-ditertbutyl-4-hydroxybenzoic acid (DHBA), to obtain a second generation of reactive additives. Those copolymers had different numbers of epoxy groups per polymer chain, and different number of epoxides opened with DHBA, hence showed a range of properties, and were utilized as reactive modifiers for polylactide (PLA) extrusion melting. The first-generation modifiers caused an increase in PLA\'s blends relative melt viscosity, stabilized material properties, and enhanced impact strength, while the second-generation modifiers with more than 8 % of epoxide ring opened showed worse properties. However, they managed to suppress the UV degradation of PLA blend plates.

Nitrogen recovery from wastewater represents a sustainable route to recycle reactive nitrogen (Nr). It can reduce the demand of producing Nr from the energy-extensive Haber-Bosch process and lower the risk of causing eutrophication simultaneously. In this aspect, source-separated fresh urine is an ideal source for nitrogen recovery given its ubiquity and high nitrogen contents. However, current techniques for nitrogen recovery from fresh urine require high energy input and are of low efficiencies because the recovery target, urea, is a challenge to separate. In this work, we developed a novel fresh urine nitrogen recovery treatment process based on modular functionalized metal-organic frameworks (MOFs). Specifically, we employed three distinct modification methods to MOF-808 and developed robust functional materials for urea hydrolysis, ammonium adsorption, and ammonia monitoring. By integrating these functional materials into our newly developed nitrogen recovery treatment process, we achieved an average of 75 % total nitrogen reduction and 45 % nitrogen recovery with a 30-minute treatment of synthetic fresh urine. The nitrogen recovery process developed in this work can serve as a sustainable and efficient nutrient management that is suitable for decentralized wastewater treatment. This work also provides a new perspective of implementing versatile advanced materials for water and wastewater treatment.

According to the 12 principles of green chemistry, surface functionalization was performed using glutaric anhydride under solvent-free and catalyst-free conditions. FTIR spectra and DS analyses demonstrated the functionalization of HCl-hydrolyzed cellulose. The influence of two parameters, i.e., the glutaric anhydride concentration and the reaction time, on the functionalization of HCl-hydrolyzed cellulose was investigated. Protocol efficiency was studied by a degree of substitution (DS). It was found that higher concentrations of glutaric anhydride cause an enhancement of DS to 0.75 and 0.87 for GA3-12 and GA9-12, respectively. In addition, the longer reaction time increased zeta potential from -12.2 ± 1.7 for G9-6 to -34.57 ± 2.2 for GA9-12. Morphology analysis by SEM showed a decrease in fiber length for the functionalized cellulose. DSC profiles confirmed dehydration at a range of 17 to 134 °C. A glass transition was revealed at -30 to -20 °C for all studied samples. The fusion, the depolymerization of cellulose chains, the cleavage of glycosidic linkages, and the decomposition of the crystalline parts of cellulose occur at 195 to 374 °C. Therefore, an efficient and greener process was developed to functionalize the HCl-hydrolyzed cellulose by glutaric anhydride, a safe and non-toxic anhydride, in the absence of the solvent and catalyst.

The separation of tellurium from cadmium telluride is examined using a unique combination of mild, anhydrous chlorination and complexation of the subsequent tellurium tetrachloride with 3,5-di-tert-butylcatecholate ligands (dtbc). The resulting tellurium complex, Te(dtbc)2 , is isolated in moderate yield and features a 103 to 104 reduction in cadmium content, as provided by XRF and ICP-MS analysis. Similar results were obtained from zinc telluride. A significant separation between Te, Se, and S was observed after treating a complex mixture of metal chalcogenides with this protocol. These three tunable steps can be applied for future applications of CdTe photovoltaic waste.