Sustainable protein/polysaccharide aerogel for the simultaneous and efficient removal of multiple organic contaminants: Insights from DFT calculations and phenomenological mass-transfer modeling.

Wastewater contains various organic contaminants that pose great hazards to human health and the environment. A protein/polysaccharide-derived aerogel, namely, ICMA, was developed as a high-performance adsorbent for the simultaneous and efficient removal of diverse contaminants from wastewater, including melanoidin (MLE), Congo red (CR), and diclofenac (DIC). Metal organic framework (UiO-66-NH2), as a regulatory factor, significantly improved the porosity and pore volume of the ICMA to enhance the capture performance of contaminants. The ICMA exhibited outstanding adsorption efficiency owing to the incorporation of ample polyamine functional groups and its well-developed pore structure, large porosity and pore volume, and remarkable heat resistance. The equilibrium capture capacities of the ICMA were 1364, 2031, and 539 mg/g for MLE, CR, and DIC, respectively, with corresponding removal efficiencies all exceeding 90%. Furthermore, the ICMA can capture cationic dyes through MLE/CR/DIC-bridging interactions. After five cycles, the used ICMA can still maintain a high contaminant removal rate/amount, demonstrating good reusability. The classic adsorption model showed that the capture of contaminants by the ICMA is a double-layered and heterogeneous adsorption orientation. A brand new LWAMTM model demonstrated that the adsorption mass-transfer process is jointly determined by the external mass conveyance, pore diffusion, and adsorption on the active site. Multiple characterizations indicated that the contaminant adsorption onto the ICMA was mainly facilitated by charge interactions, with H-bonds playing a secondary role. Quantum chemical theory simulations further provide insights into the atomic-level mechanisms involved in the capture of contaminants. Hirshfeld surface analysis revealed that the ICMA functions as both an H-bond acceptor and a donor during contaminant adsorption. Scale-up and upgrade adsorption were performed to treat actual/simulated wastewater, establishing the groundwork for the industrial implementation of the ICMA.

Polyethyleneimine-functionalized magnetic sugarcane bagasse cellulose film for the efficient adsorption of ibuprofen.

Polyethyleneimine-modified magnetic sugarcane bagasse cellulose film (P-SBC/Fe3O4 film) was simply fabricated for the removal of ibuprofen (IBP), a typical emerging organic contaminant. The P-SBC/Fe3O4 film exhibited an equilibrium adsorption amount of 370.52 mg/g for IBP and a corresponding removal efficiency of 92.63 % under following adsorption conditions: 318 K, pH 4, and 0.25 mg/mL dosage. Thermodynamic studies indicated that adsorption of IBP on the P-SBC/Fe3O4 film was spontaneous (∆G < 0) and endothermic (∆H > 0). The adsorption data conformed to the Freundlich isotherm model and multilayer adsorption model (two layers), and an average of 3-4 active sites on the P-SBC/Fe3O4 film share an IBP molecule. Both the EDR-IDR and AOAS models vividly described the dynamic characteristics of adsorption process. Model fitting results, theoretical calculations, and comprehensive characterization revealed that adsorption is driven by electrostatic interactions between the primary amine of P-SBC/Fe3O4 film and the carboxyl group of IBP molecule, while other weak interactions are also non-ignorable. Furthermore, quantitative calculations based on density functional theory (DFT) underscored the importance of PEI functionalization. In conclusion, P-SBC/Fe3O4 film is an environmentally friendly and cost-effective adsorbent with significant potential for effectively removing IBP, while maintaining its efficacy over multiple cycles.

High capacity and selective adsorption of Congo red by cellulose-based aerogel with mesoporous structure: Adsorption properties and statistical data simulation.

Large quantities of organic dyes are discharged into the environment, causing serious damage to the ecosystem. Therefore, it is urgent to develop inexpensive adsorbents to remove organic dyes. A novel cellulose-based aerogel (MPPA) with 3D porous structure was prepared by using cassava residue (cellulose) as basic construction blocks, doping ferroferric oxide (Fe3O4) for magnetic separation, and applying polyethyleneimine (PEI) as functional material for highly efficient and selective capture of Congo red (CR). MPPA exhibited porous network structure, numerous active capture sites, nontoxicity, high hydrophilicity, and excellent thermal stability. MPPA showed superior adsorption property for CR, with an equilibrium adsorption capacity of 2018.14 mg/g, and still had an adsorption property of 1189.31 mg/g after five recycling procedures. In addition, MPPA has excellent selectivity for CR in four binary dye systems. The adsorption behavior of MPPA on CR was further explored using a multilayer adsorption model, EDR-IDR hybrid model and AOAS model. Electrostatic potential and independent gradient models were used to further verify the possible interaction between MPPA and CR molecules. In conclusion, MPPA is a promising adsorbent in the field of treating anionic dyes.

Micro-mechanism insights into the adsorption of anionic dyes using quaternary ammonium-functionalised chitosan aerogels.

The development of adsorbents with outstanding adsorption capacities, wide versatility, and excellent recyclability for the removal of organic dyes remains a challenge. In this study, a quaternised chitosan-based aerogel (QCSA) was fabricated via a facile method to effectively treat concomitant anionic dyes. Porous QCSA with high hydrophilicity, nontoxicity, excellent thermal stability, and sustainability exhibits adsorption properties superior to most previously reported adsorbents. The equilibrium adsorption capacities for Congo red, Sunset yellow, and Methyl orange were 1259.6, 550.2, and 607.5 mg/g, respectively. Notably, the spent QCSA exhibits excellent cyclic performance. The multilayer adsorption, external-internal mass transfer resistance, and adsorption on the active site models were employed to enable a more accurate description of the dynamic characteristics, confirming that double-layer chemisorption was the dominant process. A quantitative analysis of the electrostatic potential and the independent gradient model further verified that electrostatic interactions, hydrogen bonding, and van der Waals forces led to the highly efficient adsorption of dye molecules. Therefore, the eco-friendly and recyclable QCSA is a promising adsorbent for trapping anionic dyes from aquatic systems.

Hyperbranched polyethyleneimine-functionalised chitosan aerogel for highly efficient removal of melanoidins from wastewater.

Melanoidins are hazardous dark-coloured substances contained in molasses-based distillery wastewater. Adsorption is an effective approach to eliminate melanoidins from wastewater. However, melanoidin adsorption capacities of available adsorbents are unsatisfactory, which seriously limits their practical application. A hyperbranched polyethyleneimine-functionalised chitosan aerogel (HPCA) was fabricated as an effective adsorbent for melanoidin scavenging. HPCA demonstrated superior melanoidin adsorption efficiency because of its high specific surface area, abundant amino functional groups, and high hydrophilicity. Melanoidin removal rate of HPCA was 94.95%, which remained at 91.45% after 5 cycles. Notably, using the Langmuir isothermal model, the maximum melanoidin adsorption capacity of HPCA was determined to be 868.36 mg/g, surpassing those of most of previously reported adsorbents. Toxicity experiments indicated that HPCA can be considered a safe adsorbent with excellent biocompatibility that hardly threatens aquatic organisms. The efficient melanoidin removal of HPCA was attributed to electrostatic attraction, H-bonding, and van der Waals force. However, the adsorption might be predominantly controlled by electrovalent interaction between protonated amino groups of HPCA and carboxyl/carboxylate groups of melanoidins. Two novel models, namely, external diffusion resistance-internal diffusion resistance mixed model and adsorption on active site model, were employed to describe the dynamic mass transfer characteristics of melanoidin adsorption by HPCA.

(3-Chloro-2-hydroxypropyl) trimethylammonium chloride and polyethyleneimine co-modified pomelo peel cellulose-derived aerogel for remelt syrup decolorization in sugar refining.

The crucial need for quality refined sugar has led to the development of advanced adsorbents, with a focus on the decolorization of remelt syrup. In this study, (3-chloro-2-hydroxypropyl) trimethylammonium chloride and polyethyleneimine co-modified pomelo peel cellulose-derived aerogel (CP-PPA) was fabricated, and synthetic melanoidins were used as model colorants of remelt syrup to evaluate the validity and practicality of CP-PPA for eliminating colored impurities. Integrating abundant amine-functionalized groups (quaternary ammonium and protonated amine) within the pomelo peel-derived aerogel directionally captured electronegative melanoidins via electrostatic interactions. Furthermore, the active sites, types, and relative strength of the weak interactions between CP-PPA and melanoidins were determined using density functional theory simulations. CP-PPA exhibited an excellent equilibration adsorbing capacity for capturing melanoidins of 749.51 mg/g, and a removal efficiency of 93.69 %. Additionally, the adsorption mechanism was thoroughly examined in an effort to improve the economy of the sugar refinement industry.