This study developed an oleic acid (OA)-functionalized, bio-derived calcium carbonate (Bio-CaCO3) filler recovered from Asian green mussel (Perna viridis) shell waste for incorporation into a hydroxypropyl methylcellulose (HPMC)-glycerol (Gro) matrix as a hydrophobic composite coating for reducing pesticide deposition on mandarin surfaces. Aragonite-rich Bio-CaCO3 was extracted through a combined chemical treatment and mechanical pulverization process. The extracted Bio-CaCO3 was characterized by scanning electron microscopy, X-ray diffraction, laser diffraction, and ATR FT-IR spectroscopy. At the optimal OA concentration, surface functionalization yielded OA-functionalized Bio-CaCO3 (OA-Bio-CaCO3) powder beds that exhibited apparent superhydrophobicity; successful functionalization was confirmed by X-ray photoelectron spectroscopy. The resulting HPMC-Gro-OA-Bio-CaCO3 coating dispersion (CD-OA) formed hydrophobic composite films (f-CD-OA), as demonstrated by water contact-angle measurements and surface-morphology analysis. The CD-OA coating formulation was successfully applied to mandarin surfaces by a dip-coating process. Colorimetric screening indicated that organophosphate pesticide residues on coated mandarins did not exceed hazardous levels, even at 20 times the manufacturer-recommended application rate. Quantitative LC-MS/MS and GC-MS/MS analyses demonstrated that the optimized CD-OA coating formulation provided substantial short-term protection against acetamiprid and chlorothalonil with pesticide-deposition reductions of 89% and ≥96%, respectively, after 1 d relative to pristine mandarins. These findings advance the functional reuse of biogenic CaCO3 and offer a simple, water-based dip-coating approach that provides temporary surface protection for citrus production and food-safety management.
Ibuprofen- and diclofenac-loaded organobentonites are thermally converted to carbon-decorated bentonites and probed as materials for supercapacitors and peroxide production. TGA shows a ~40% mass loss in an inert atmosphere and a ~2% further reduction in air, with the diclofenac-loaded sample showing slightly higher loss due to less stable surface groups. FTIR and Raman spectroscopies indicate similar surface groups and defect densities in the end materials, which are reflected in similar electrochemical responses. Capacitance values of around 20 F/g are measured when taking the whole mass, bentonite and carbon, into account, rising to a maximum of 805 F/g if only the carbon fraction is taken into account. Rotating ring–disk measurements reveal that the prepared materials show selectivity toward peroxide production when oxygen reduction is probed, reaching a 93% yield, making it an exceptional candidate for peroxide production.
The ordered copper-based intermetallic compound Cu0.83Si0.17 is capable of enhancing the catalytic efficiency of the in-demand green process of the electrochemical reaction of ammonia synthesis from nitrite in comparison with a pure copper metal catalyst, which is well known and studied. The Faradaic efficiency reaches 99% with its maximum at a potential of −0.525 V (RHE), and even at low potentials (−0.1 V) it does not fall below 90%, with an NH3 yield rate of 132.3 µmol h−1 cm−2. In addition, the catalyst demonstrated high selectivity and stability.
Plastic waste presents a persistent environmental burden, yet its constituent polymers represent structurally valuable chemical feedstocks. Mechanical recycling remains limited due to polymer degradation, additive contamination, and material downcycling, underscoring the need for alternative strategies. Chemical upcycling offers pathways to convert post-consumer plastics into higher-value monomers, functional chemicals, and bioactive or pharmaceutical precursors by exploiting inherent structural motifs such as aromatic rings, ester linkages, and heteroatom-containing backbones. Approaches such as catalytic depolymerization, molecular functionalization, microbial and enzymatic transformation, and scaffold repurposing enable the recovery of polymer-derived building blocks with improved functional value. Case studies illustrating the conversion of discarded plastics into advanced materials and biologically relevant small molecules demonstrate the potential of these approaches to stimulate innovation and expand sustainable chemical practices. Collectively, such developments align with green chemistry principles, support emerging circular chemical economies, and contribute to global sustainability priorities reflected in the United Nations Sustainable Development Goals. This review aims to outline the guiding principles of chemical upcycling and highlight the challenges in chemical design, encouraging the modern chemistry community to tap into the hidden potential of waste plastics.
Libidibia coriaria (Cascalote), an underutilized leguminous species native to the tropical Americas, is a promising source of bioactive phenolic compounds with pharmaceutical and nutraceutical potential. This study compared microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE), and their hybrid combination (UMAE) for the recovery of hydrolyzable and condensed phenolics from cascalote pods and evaluated the antioxidant capacity of the resulting extracts. UMAE achieved the highest total phenolic content (223.49 mg GAE/g dry matter), while antioxidant capacity varied by assay: MAE showed the highest DPPH radical scavenging activity and FRAP reducing power, whereas UAE exhibited the highest ABTS radical-scavenging activity. Nevertheless, UMAE showed the lowest IC50 values for DPPH and ABTS (228.91 and 155.65 mg/L, respectively), indicating greater concentration-dependent radical-scavenging efficiency. Qualitative HPLC–MS tentatively identified gallotannins, ellagitannins, and hydroxybenzoic acid derivatives. UAE yielded the broadest phenolic profile, whereas MAE and UMAE shared several major tannin-related compounds. FTIR analysis supported the presence of characteristic functional groups associated with gallotannins and ellagitannins. Overall, under the evaluated conditions, UMAE was the most effective extraction method for improving phenolic recovery. These findings highlight the potential of this hybrid extraction approach for the valorization of L. coriaria pods as a source of high-value bioactive phenolic compounds.
Sample preparation is frequently a time-consuming process and can be a major bottleneck in many analytical techniques that involve some form of modification to a sample so that it can be analyzed without interference or to increase its sensitivity. As part of the movement towards “green analytical chemistry”, the reduction in organic solvent usage and toxicity via alternative solvents compared to those traditionally used in analytical chemistry has gained increasing interest. Although ionic liquids were thought to have limitations, deep eutectic solvents (DESs) are being looked at as alternatives to traditional organic solvents in analytical chemistry because of their ability to produce a “tunable” set of physico-chemical properties that enable the selective and efficient extraction of a wide variety of analytes from a very diverse array of matrices. Although deep eutectic solvents have attracted increasing attention in analytical extraction applications, a systematic comparison of their performance across various extraction techniques is still lacking. This review fills this gap by offering a comprehensive and integrated evaluation of DES-based extraction approaches, emphasizing the interdependence between solvent characteristics, extraction efficiency, selectivity, and sustainability. The insights presented herein are intended to support the rational selection of appropriate DES-based extraction strategies for diverse analytical purposes. Moreover, these findings are expected to contribute to the advancement of greener, more efficient sample preparation methodologies within the field of green analytical chemistry. In this review article, we describe several analytical chemistry techniques that utilize DESs, such as dispersive liquid–liquid microextraction, solid-phase extraction, ultrasound-assisted extraction, etc., and explain the basic principles and mechanisms behind each technique. Additionally, comparative evaluations are provided to identify the relative advantages and disadvantages of the techniques mentioned above in terms of extraction efficiency and selectivity, and speculation regarding future trends and challenges in DES-based extraction systems will also be included. By integrating recent advances and comparative performance assessments, this review serves as a reference for researchers and industry practitioners, fostering innovation and promoting the wider adoption of sustainable extraction technologies.
Electrochemical conversion of carbon dioxide (CO2) to ethanol offers a potential route for integrating carbon utilization with low-carbon electricity; however, its environmental performance is governed by the complete process system rather than by catalytic selectivity alone. This study presents a detailed attributional cradle-to-gate life cycle assessment of anion-exchange-membrane (AEM) and bipolar-membrane (BPM) electrolyzer systems using a functional unit of 1 kg of ethanol at the plant gate. The foreground inventory combines stoichiometric balances, peer-reviewed electrochemical evidence, process-energy estimates, and transparent engineering assumptions, while background processes are represented using ecoinvent 3.7.1. Climate-change impacts are evaluated with the IPCC 2021 100-year global warming potential method. The modeled AEM and BPM systems require 23.32 and 27.92 kWh of electricity per kilogram of ethanol, respectively. Wind-powered operation yields the lowest reported impacts, at 0.318 kg CO2-eq kg−1 ethanol for AEM and 0.442 kg CO2-eq kg−1 for BPM. Photovoltaic scenarios yield 1.812 and 2.231 kg CO2-eq kg−1, whereas the Austrian-grid scenarios yield 1.349 and 4.686 kg CO2-eq kg−1, respectively. Electricity supply is the dominant environmental driver, while separation heat, carbon utilization, component lifetime, and oxygen co-product treatment remain important secondary parameters. The BPM Austrian-grid result is disproportionately high relative to the 19.7% increase in modeled electricity demand and therefore requires exchange-level verification before it can be interpreted as a physical membrane effect. Overall, environmentally credible CO2-to-ethanol deployment requires low-carbon electricity, reduced cell voltage, efficient carbon management, concentrated product streams, durable components, and transparent co-product accounting.
Bio-derived functional materials are key platforms for long-term sustainable environmental remediation. Pine wood fibres (WF) is an abundant and renewable material with functional properties suited to specialized applications, including a high density of hydroxyl groups at its surface and mechanical toughness imparted by the lignin fraction. In the present work, monometallic and bimetallic nanoparticles (NPs) of first series transition metals, Fe, Co, Cu and Fe/Cu were immobilized onto original WF and WF treated with NaOH (WF_N). The prepared WF-supported NPs were characterized by SEM/EDS, XPS, XRD and FTIR-ATR and evaluated in the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol in aqueous solution, at room temperature, by NaBH4. Copper-based materials exhibited superior catalytic efficiency, with the NaOH pre-treatment yielding shorter induction times and enhanced stability. For material WF_NCu, 97 % of 4-NP reduction was achieved in 3 minutes with a rate constant of k1 = 2.209 min-1. This material was used for five successive cycles with no decrease in 4-NP reduction efficiency, being easily recovered from reaction media.
The contamination of aquatic environments by cadmium and other toxic heavy metals represents a major environmental concern requiring efficient and operationally sustainable remediation strategies. In this work, iron oxide materials were synthesized through a microwave-assisted hydrothermal method and evaluated for Cd(II) removal from aqueous systems. Different precursor compositions and organic additives were initially screened in order to identify the most suitable adsorbent formulation. The selected Fe-Tart material was characterized by FTIR, SEM-EDS, and XRD analyses, revealing hydroxylated and poorly crystalline iron oxide structures with heterogeneous surface organization. Batch adsorption experiments were performed under controlled conditions to investigate the influence of pH and equilibrium adsorption behavior, while adsorption data were analyzed using Langmuir and Freundlich isotherm models. Cd(II) uptake showed strong pH dependence, with adsorption progressively increasing from acidic to near-neutral conditions and reaching approximately 80% removal at pH 7–8. The Langmuir model provided the best fitting results (R2 = 0.988), suggesting preferential occupation of energetically comparable surface sites with a maximum adsorption capacity of 6.51 mg g−1. The adsorption behavior was interpreted within a pH-dependent surface complexation framework involving hydroxylated iron oxide surfaces. Although the adsorption capacity remained lower than that reported for some highly engineered adsorbents, the results indicate that microwave-assisted synthesis may provide a relatively simple and rapid route for preparing iron oxide-based materials potentially applicable to water remediation systems.
Ruthenium possesses outstanding properties and is widely utilized in many fields. However, its natural scarcity makes the recovery of ruthenium from waste liquids particularly important. A dendrimer-grafted chitosan adsorbent is synthesized through Michael addition and amidation reactions on chitosan, which is then used to adsorb Ru(III) from aqueous solutions. Compared with unmodified chitosan, this adsorbent has abundant binding sites and can rapidly and efficiently adsorb Ru(III) through electrostatic attraction and complexation. Characterization techniques, including FT-IR, XPS, and SEM, confirmed successful modification. Adsorption experiments show that this adsorbent exhibits an adsorption efficiency of up to 97.79% for Ru(III) and saturated adsorption capacity of 162 mg/g. The results of competitive adsorption experiments demonstrate that the adsorbent has good selectivity for Ru(III), retaining 71.22% of adsorption efficiency after five cycles. This work offers a new possibility for the environmentally friendly and efficient recovery of Ru(III) from wastewater.
Electrochemical CO2 reduction to ethanol is a promising route for circular carbon fuel and chemical production, but practical implementation remains limited by coupled membrane, catalyst, transport, and system integration constraints. This Communication reassesses anion-exchange membranes (AEMs) and bipolar membranes (BPMs) for CO2-to-ethanol electroreduction by integrating recent 2024–2026 advances with foundational membrane and CO2RR literature. The central argument is that membrane selection is not a passive separation choice; instead, it actively controls local pH, charge carriers, CO2 availability, carbonate formation, water activity, proton/cation delivery, product crossover, and downstream techno-economic assessment (TEA) and life-cycle assessment (LCA) burdens. AEM operation can create alkaline cathodic microenvironments that favor C–C coupling, but bicarbonate/carbonate formation imposes carbon-loss, salt-management, and CO2-recovery penalties. BPM operation can improve pH separation and carbon management through water dissociation and bicarbonate acidification, but its viability depends on water-dissociation efficiency, co-ion exclusion, junction stability, hydration management, and voltage control. Recent ethanol-selective catalyst studies further show that copper oxidation state, grain boundaries, subsurface dopants, ionomers, interfacial wettability, and dynamic operation interact strongly with membrane-imposed microenvironments. This Communication proposes a membrane-centered decision framework linking AEM/BPM selection with ethanol selectivity, single-pass carbon utilization, energy efficiency, durability, TEA/LCA boundaries, and future reactor design.
Cellulose crystallinity is frequently associated with lignocellulosic biomass digestibility, yet its development during multistep biorefinery processing and its relationship with enzymatic hydrolysis remain difficult to isolate. This study investigated the evolution of cellulose crystallinity in wheat straw (Triticum aestivum) during Hot-Water Pretreatment (HWP), Water Pretreatment (WP), Organosolv extraction, sequential washing, and drying, and related these changes to enzymatic glucose yield. Crystallinity was determined using X-ray diffraction and an ATR-FTIR-based PLS model, while enzymatic hydrolysis was evaluated by HPLC-based glucose quantification. HWP caused a temperature-dependent decrease in crystallinity from 47.5 ± 1.3% in untreated straw to 27.0 ± 2.2% at 120 °C, whereas WP at room temperature caused no significant change. However, without subsequent Organosolv extraction, both pretreatments alone resulted in low glucose yields of approximately 10%, indicating that cellulose crystallinity is only one of several factors governing enzymatic hydrolysis efficiency. During washing after Organosolv extraction, crystallinity increased from 40.6 ± 2.1% to 54.2 ± 1.3%, whereas, under the tested conditions, glucose yield was more closely associated with the estimated residual ethanol concentration than with the change in crystallinity. Drying had the strongest effect, increasing crystallinity by up to 53.6% relative to the wet state. Overall, cellulose crystallinity should be considered as one of several interacting factors governing enzymatic digestibility, and sample moisture history must be carefully controlled when comparing crystallinity data.
Deep eutectic solvents (DESs) have undergone a remarkable transformation over the past two decades, evolving from a laboratory curiosity into one of the most actively investigated solvent platforms in green chemistry. Yet, despite this rapid expansion, and although the field is well served by numerous topical reviews, it still lacks a corpus-wide, cross-disciplinary synthesis capable of guiding strategic research priorities, identifying critical knowledge gaps, and informing policy and industrial investment decisions. The present work addresses this need through a thorough analysis of global DES research from 2003 to 2025, based on a deduplicated corpus of 17,757 publications retrieved from the Web of Science Core Collection and Scopus following PRISMA-adapted screening guidelines. The analysis maps temporal publication dynamics, geographic and institutional contributions, thematic evolution, journal landscape, component usage patterns, international collaboration networks, market projections, and alignment with the United Nations Sustainable Development Goals. The results document an exponential growth trajectory—from a single publication in 2004 to 3954 in 2025 (CAGR > 30%)—and reveal a clear thematic transition from early electrochemistry-dominated research toward extraction, pharmaceutical, and environmental applications, with machine-learning-assisted design and hydrophobic DES formulations emerging as the most dynamic current frontiers. China leads global output with 6819 publications (38.4%), while the United States and Malaysia achieve the highest citation-per-publication ratios among the leading nations (≈46.7 and ≈38.9, respectively, versus ≈27.6 for China), and Spain pairs a comparatively modest output with a high h-index, indicating that impact is large relative to volume. Type III DESs and NADESs collectively account for approximately 69% of the literature, with choline chloride present in 72% of reported formulations. The global DES market, valued at approximately USD 166 million in 2024, is projected to reach USD 370 million by 2030. Despite this progress, critical translational barriers persist: fewer than 0.3% of publications include techno-economic or life cycle assessment analysis, standardized characterization protocols remain absent, and toxicological datasets are systematically incomplete. This panoramic analysis is intended to serve as an evidence-based reference for researchers prioritizing future directions, for funding agencies assessing the maturity and needs of the field, and for industrial stakeholders evaluating the readiness of DES technologies for scale-up.
This study investigates the synthesis of La0.6Ca0.4FeO3 (LCF) perovskite via a ball milling method for application in reverse water–gas shift chemical looping (RWGS-CL) for CO2-to-CO conversion. Unlike conventional wet-chemical routes such as the Pechini method, the ball milling approach offers a solvent-free, scalable synthesis using low-cost metal oxide precursors (e.g., La2O3, CaO, Fe2O3). Structural analysis by XRD confirmed the successful formation of single-phase cubic perovskite, with no secondary phases when using oxide precursors. Crystallite size increased with calcination temperature, from 118.9 Å (no calcination) to 404.3 Å (1050 °C). BET analysis revealed a decrease in surface area from 2.5 m2/g (no calcination) to 0.51 m2/g (1050 °C), consistent with sintering at higher temperatures. TPR-H2 and TPO-CO2 studies revealed that non-calcined LCF possesses slightly enhanced redox properties, with oxygen vacancy formation and CO2 reoxidation activity both at 500 °C. RWGS-CL experiments demonstrate that all LCF samples exhibit stable CO production (910–970 µmol/gLCF) over multiple cycles at 500 °C, with comparable performance across calcination conditions. A cost and sensitivity analysis reveals that the ball milling method had lower synthesis costs by approximately 92% at the laboratory-scale and 88% at the industrial-scale compared to the Pechini method, highlighting its strong potential for large-scale perovskite production.
In recent years, there has been growing awareness of the potential harmful effects that analytical methods can have on human health and the environment. Green analytical chemistry (GAC) integrates sustainability into chemical analysis by emphasizing a reduction in waste, energy consumption, and hazardous reagents while maintaining analytical performance. This review summarizes the most recent developments in atomic spectrometry techniques used for analyzing trace metals in various types of samples. Key advances include green metrics, sampling methods, direct analysis, and instrument miniaturization. Since direct sample analysis via spectrometric methods is rarely feasible, recent developments in sample pretreatment, which align with the 12 principles of GAC, are also discussed. Passive sampling can serve as a valuable approach for conducting analyses with reduced sample pretreatment steps and overall costs, thereby addressing these concerns. Current green assessment metrics and their application in atomic spectrometry are also reviewed. This article aims to provide researchers with detailed information to improve the determination of trace metals in accordance with GAC principles.
This study explores the use of microwave-assisted extraction of bioactive compounds from peppermint (Mentha piperita L.) using aqueous ethanolic and β-cyclodextrin solvents. The experiments were performed according to Response Surface Methodology, and the central composite design was employed, with the independent variables being treatment time, microwave power and solvent concentration. During the research, the total polyphenol content (TPC, expressed as gallic acid equivalents, GAE), total flavonoid content (TFC, expressed as quercetin equivalents, QUE), antioxidant capacity (AC) using the FRAP (Ferric Reducing Antioxidant Power, expressed as ascorbic acid equivalents, ASE) and DPPH (2,2-diphenyl-1-picrylhydrazyl) methods, and total menthol content (TMC, expressed as menthol equivalents, MEE) were examined. For the ethanolic extraction, the optimum conditions were 571 W, 7.3 min, and 10% v/v. The following results were obtained for these parameters: TPC, 1025 µg GAE/mL; TFC, 66.69 µg QUE/mL; FRAP, 3786.24 µg ASE/mL; DPPH, 80.24%; and TMC, 62.63 µg MEE/mL. In the case of β-cyclodextrin, the optimum conditions are 800 W, 11.81 min, and 1.70 mM. In this case, the results are as follows: TPC, 949.29 µg GAE/mL; TFC, 90.75 µg QUE/mL; FRAP, 4275.54 µg ASE/mL; DPPH, 89.81%; and TMC, 84.99 µg MEE/mL. β-cyclodextrin increased the flavonoid, antioxidant and menthol content, although there were no significant differences between the concentrations. The use of ethanol had a greater effect on the polyphenol content. β-cyclodextrin proved to be an effective green alternative solvent for peppermint.
Wheat straw is an abundant agricultural residue with high potential for carbohydrate-based bioconversion, yet its efficient utilization is limited by lignocellulosic recalcitrance. This study systematically investigated Organosolv extraction of wheat straw (Triticum aestivum) with the goal of achieving near-complete enzymatic hydrolysis at minimized process severity and energy demand. Process severity was evaluated using the P-Factor concept. In preliminary screening, acid catalysts and liquor ratios were assessed. Strong acids clearly outperformed weak acids: at comparable severity, 5% (w/w, DM) H2SO4 or p-toluenesulfonic acid (PTSA) yielded glucose yields of 83 ± 2.4% and 81 ± 6.2%, respectively, whereas weak acids (phosphoric, lactic, acetic) and a catalyst-free control resulted in only ~20–41% glucose yield. Liquor ratio strongly affected extraction performance; a ratio of 1:19 provided the highest glucose yield (85 ± 1.4%) and robust mixing compared to 1:12–1:15 (67–68%). Two novel pretreatment strategies applied prior to Organosolv extraction, namely Hot-Water Pretreatment (HWP) and Water Pretreatment (WP), significantly increased hydrolysability compared to untreated straw (58 ± 3%), reaching 79 ± 2% for HWP and 86 ± 5% for WP. DoE-based experiments (135–170 °C; P-Factor 3.0–4.0) showed that increasing temperature from 135 to 150 °C markedly improved hydrolysability (e.g., WP: 74 ± 3% to 96 ± 3%), while further increasing to 170 °C provided no additional benefit. Response-surface modeling predicted a maximum hydrolysability of approximately 88% for HWP but complete hydrolysis for WP within 152–170 °C, indicating a broad operational window. Overall, combining simple Water-based Pretreatment with severity-optimized Organosolv extraction enables energy-efficient, near-complete hydrolysis at lower operating temperatures, reducing both energy demand and pressure requirements, and thereby offering advantages in process cost and scalability.
The avocado oil industry discards residues from the peeling and destoning steps primarily as mixtures with high biofunctional potential. Extracts from a residual avocado oil industry (RAOI) mixture were evaluated for the effects of green technologies Naviglio® (rapid solid–liquid dynamic extraction), ultrasound, and maceration on their functional compounds and biological activity. The Naviglio® extract excelled for total flavonoid content (7.29 ± 1.09 mg QE/g), minimum inhibitory concentration (MIC) against Escherichia coli (25 mg/mL) and Staphylococcus aureus (25 mg/mL), and minimum bactericidal concentration (MBC) against Staphylococcus aureus (50 mg/mL), with similar anti-inflammatory activity and total phenolic content (17.32 ± 0.59 mg GAE/g) than the maceration extract. Maceration was superior in seven polyphenol contents, β-sitosterol (9135.87 ± 468.83 mg/kg), and antioxidant activities (116.71 ± 16.09, 63.85 ± 3.97 and 49.63 ± 1.83 µmol TE/g for ABTS, FRAP and DPPH, respectively). At the evaluated MIC and MBC, the Naviglio® extract was non-toxic, while maceration and ultrasound extracts were moderately toxic; at the anti-inflammatory concentrations tested, the Naviglio® and ultrasound extracts were non-toxic. Naviglio® and ultrasound extracts have pharmaceutical potential as antioxidants and anti-inflammatory agents, while the macerated extract is a potential source of β-sitosterol. For the first time, Naviglio® technology was applied to RAOI mixtures, and the biological properties of the extracts were evaluated.
The adsorption and activation of CO2 on CuxScy nanoclusters with x + y equal to 4 were analyzed using DFT and PDOS and TDOS signatures. The geometries of Cu3Sc, Cu2Sc2, and CuSc3 were optimized in the gas phase, and the minima were verified by frequencies in ORCA using M06-2X/def2-TZVP. Multiplicities 1, 3, and 5, temperatures between 298 and 400 K, and four CO2 coordination modes R1 to R4 were evaluated. Naked and complex cluster comparison panels were constructed, and two energy windows, −18 to −10 eV and −8 to 6 eV around the Fermi level, were analyzed, complemented by frontier orbitals and charge maps. Thermodynamics indicated that mode and multiplicity control the adsorption energy, with ANOVA p-values of 0.002 and 0.008, while temperature was not significant (p = 0.682). In Cu3Sc–C2v(1), the R1 singlet at 298 K showed Eads −33.43 kcal·mol−1 with spin contamination, while alternative modes in the singlet were unfavorable. In PDOS and TDOS, the bare cluster exhibits a Cu d band at −11 to −10 eV and a valley around −5 eV. The exergonic complexes show CO2 signals near the Fermi level, superimposed on Cu and Sc states, with state filling and broadening. Transferable indicators based on CO2 intensity in the −8 to 6 eV range and metal–adsorbate overlap are proposed as predictors of exergonic adsorption.
This study aimed to improve the mechanical integrity of Styrofoam membranes fabricated from post-consumer food packaging. To this end, 3D-printing byproduct—thermoplastic polyurethane (TPU) waste—was blended with polyimide (PI) in the membrane dope solution. The synthesized flat-sheet upcycled membranes were evaluated via scanning electron microscopy (SEM), water contact angle (WCA), and tensile testing, while separation efficiency was determined through bovine serum albumin (BSA) rejection and permeation trials. Findings indicate that incorporating TPU into the Styrofoam/PI matrix increased tensile strength by 50%, BSA rejection by 12.4%, and permeation by 33%. Compared with pristine Styrofoam membranes, tensile strength and BSA rejection improved by 240% and 46%, respectively. Although the blend membranes exhibited a reduction in water flux (from 214 to 162.5 LMH/bar) due to pore contraction, they maintained high rejection rates (~86%) for large macromolecules like PVP (1300 kDa). Furthermore, while all membranes remained hydrophilic, hydrophobicity scaled with TPU concentration.
