Concentration Of Acid Groups Research Articles

Fractionation of Kraft Lignin for Production of Alkyd Resins for Biobased Coatings with Oxidized Lignin Dispersants as a Co-Product.

A new valorization pathway based on solvent fractionation was applied to kraft lignin, a major by-stream of the pulping industry, to extract a soluble lignin intermediate featuring an improved structural homogeneity, a low molecular weight, and a high content of phenolic hydroxyl and carboxylic acid groups to serve as a substitute of the nonrenewable polyacids in the formulation of alkyd resins, a dominant material used in the production of anticorrosion surface coatings. Herein, softwood kraft lignin was mixed in a low-cost green solvent, aqueous ethanol, prepared at different ratios, at room temperature to generate a soluble fraction of a low M w of ≤2200 g mol-1 and an insoluble fraction of a high M w of ≥3950 g mol-1 of lignin. The best combination of yields and molecular weights of soluble lignin (16-36% yield, 1740-1890 g mol-1) was attained using 50-80 vol % ethanol in fractionation. Thus, these conditions were further employed at the pilot scale to demonstrate the scalability of this technology. Soluble lignin from pilot fractionation was used to produce an optimal alkyd resin formulation and thereafter an anticorrosion coating on the metal surface, both of which matched the target properties of industrial standards well (180 s Persoz hardness and 72 gloss units of coating, 100% adhesion of paint with no cracks or peeling in the cross-cut test, no corrosion after 120 h of the salt spray test). The insoluble solids from pilot fractionation could also be valorized by alkali-O2 oxidation into lignin-based dispersants for special carbon black pigments. Overall, this study presents a new, simple strategy to develop an efficient, scalable, low-cost, and green process for upgrading kraft lignin into phenolic intermediates for biobased alkyd resins to facilitate sustainable production of high-performance anticorrosion coatings.

Achievement of biochar photocatalytic performance by synergistic oxidation of sulfuric acid/hydrogen peroxide: Towards revealing the mechanism of synergistic oxidation on photocatalytic performance

The oxygen-containing functional groups of biochar have great potential in tailoring photochemical properties, but the content of oxygen-containing functional groups of pristine biochar is insufficient to support photocatalytic reactions. In this study, a synergistic oxidation of H2SO4 and H2O2 was innovatively proposed to prepare biochar photocatalysts (OGPC400). The results showed that the synergistic oxidation of H2SO4 and H2O2 increased the contents of hydroxyl and carboxyl groups of biochar with the degree of oxidation, and the total concentration of acidic functional groups was about 4 mmol/g higher than that of the oxidation with H2SO4 or H2O2 alone, which was attributed to the synergistic oxidation to promote the conversion of CH and C-OH on the benzene ring. The achievement of electron exchange among hydroxyl and carboxyl groups and internal electron transfer within biochar by the benzene ring as a medium resulted in 100 % degradation of rhodamine b (RhB) and 25 times reaction rate constant higher than that of pristine biochar, as compared to only 45 % or 37 % degradation by oxidation with H2SO4 or H2O2 alone. The exciting results confirmed the positive availability of H2SO4 and H2O2 synergistic oxidation on biochar photocatalysts, which is expected to be applied in environmental remediation.

Probing the Closed Association of Oligoquinoline Foldamers by Time-Resolved Fluorescence Anisotropy.

The metal-mediated dimerization of oligoquinoline foldamers terminated at one end with an oligo(phenylenevinylene) and at the other with a carboxylic acid (OPV-QnA, where n = 4, 8, 17, and 33), and the complexation of OPV-Q8A and Q16A was promoted in chloroform by the addition of a concentrated 16 M aqueous sodium hydroxide solution. UV-vis absorption and time-resolved fluorescence anisotropy (TRFA) experiments were conducted to determine, respectively, the concentration and the average rotational time ⟨ϕ⟩ of the mixture of unassociated and associated foldamers across a range of foldamer concentrations spanning 5 orders of magnitude. Plots of ⟨ϕ⟩ as a function of acid group concentration revealed that ⟨ϕ⟩ increased with increasing foldamer concentration only when the foldamer solution in chloroform was vigorously mixed with the 16 M sodium hydroxide aqueous solution. Furthermore, all plots showed that ⟨ϕ⟩ reached a plateau at high foldamer concentration. The increase in ⟨ϕ⟩ reflected the association of foldamers into larger objects through metal ion coordination with the carboxylate anions generated by deprotonation of the carboxylic acid of OPV-QnA with NaOH, while the plateau obtained at high foldamer concentration indicated that these interactions led to the dimerization of the foldamers via a closed association mechanism. Analysis of the ⟨ϕ⟩ trends yielded the equilibrium constants (K) describing the foldamer dimerization, whose value equaled 1.0 (±0.2) × 106 M-1 for the three longer OPV-QnA foldamers, but was about 10 times smaller for the shortest one (n = 4). Association of OPV-Q8A and Q16A yielded a complex with a ⟨ϕ⟩ matching that of OPV-Q24A, and K for this complexation was similar to that for dimerization. These experiments illustrate the robust nature of TRFA as an experimental method to probe the size of rigid, self-assembled foldamers in solution.

The Characteristics of Milk Fatty Acid Profile Predicted by Fourier-Transform Mid-Infrared Spectroscopy (FT-MIRS) in Chinese Holstein Cows.

Fatty acid is an important factor affecting the nutritional quality of milk. In this study, we collected and assessed 78,086 milk samples from 12,065 Chinese Holstein cows from 11 farms in Northern China from November 2019 to September 2022. The contents of eight fatty acid groups were predicted using FT-MIRS-based models. The contents of TFAs, SFAs, UFAs, MUFAs, PUFAs, and LCFAs in milk reached the highest at 96-125 DIM, and SCFA and MCFA contents reached the highest at 276-305 DIM. With the increase in somatic cell score, the contents of various fatty acid groups in milk gradually decreased, and the nutritional value of milk and flavor of dairy products gradually deteriorated. The contents of high-quality fatty acids in milk, particularly UFAs and MUFAs, were significantly higher in the non-pregnant state than in the pregnant state. However, SCFA and MCFA contents exhibited the opposite pattern. Our findings provided valuable information on the content and distribution range of fatty acid groups in milk from Chinese Holstein cows. Further analysis is warranted to explore the breeding of Chinese Holstein cows providing milk with abundant beneficial fatty acids.

Characterization of salt brine sulfated polysaccharides: immunomodulatory activity based on gut microbiota

A sulfated polysaccharide consisting of two components with molecular weights of 439 kDa and 16 kDa was extracted from the salt brine. The structural properties, immunomodulatory activity, in vitro fermentation behaviors, and effects of SP on regulating the gut microbiota were investigated. The chemical composition and monosaccharide composition analysis showed that the neutral sugar, protein, uronic acid, and sulfated group contents of SP were 60.42 ± 0.04%, 2.90 ± 0.01%, 13.34 ± 0.01% and 10.51 ± 0.01%, respectively, containing arabinose, galactose, glucose, rhamnose, xylose, mannose, and glucuronic acid in a molar ratio of 33.24:19.18:16.64:13.25:8.31:4.11:5.27. Results from the macrophage cell model showed that SP intervention improved the proliferation activity, phagocytosis of neutral red, and production of IL-6 and TNF-α in RAW 264.7. Furthermore, in vitro fermentation of SP by gut microbiota showed that SCFA production in all treatment groups was significantly higher than that of the blank control group after 48 h of fermentation, especially butyric acid which was 1.70 folds that of the control group. Moreover, long-term fermentation (48 h) of SP improved the diversity of microbiota, decreased the F/B ratio (30.75 at 0 h vs. 1.22 at 48 h), and promoted the growth of probiotics (Parabacteroides, Bacteroidetes, Ruminococcaceae, and Phascolarctobacterium). The positive regulatory effect of SP on the gut microbiota and its metabolites is considered a potential target for its immunomodulatory activity.Graphical abstract

Green adsorbents for pharmaceutics removal from urine: Analysis of isotherms, kinetics, adsorption interactions, cost estimation, and environmental impact

Husks of rice (RH), coffee (CH), and cholupa (CLH) were used to produce natural adsorbents. The natural adsorbents were used to remove pharmaceuticals such as diclofenac, ciprofloxacin, and acetaminophen in a mixture of distilled water. However, CH stood out for its efficiency in removing ciprofloxacin (74%) due to the higher concentration of acidic groups, as indicated by the Boehm method. In addition, CH removed 86% of ciprofloxacin individually. Therefore, CH was selected and used to remove other fluoroquinolones, such as levofloxacin and Norfloxacin. Although electrostatic interactions favored removals, better removal was observed for ciprofloxacin due to its smaller molecular volume. Then, ciprofloxacin was selected, and the effect of pH, matrix, and adsorbent doses were evaluated. In this way, using a pH of 6.2 in urine with a dose of 1.5 g L−1, it is possible to adsorb CIP concentrations in the range (0.0050–0.42 mmol L−1). Subsequently, the high R2 values and low percentages of APE and Δq indicated better fits for pseudo-second-order kinetics, suggesting a two-stage adsorption. At the same time, the Langmuir isotherm recommends a monolayer adsorption with a Qm of 25.2 mg g−1. In addition, a cost of 0.373 USD/g CIP was estimated for the process, where the material can be reused up to 4 times with a CIP removal in the urine of 51%. Consequently, thermodynamics analysis showed an exothermic and spontaneous process with high disorder. Furthermore, changes in FTIR analysis after adsorption suggest that CH in removing CIP in urine involves electrostatic attractions, hydrogen bonds and π-π interactions. In addition, the life cycle analysis presents, for the 11 categories evaluated, a lower environmental impact of the CIP removal in urine with CH than for the preparation of adsorbent, confirming that the adsorption process is more environmentally friendly than materials synthesis or other alternatives of treatments. Furthermore, future directions of the study based on real applications were proposed.

Brown Algae as a Valuable Substrate for the Cost-Effective Production of Poly-γ-Glutamic Acid for Applications in Cream Formulations.

Poly-γ-glutamic acid (γ-PGA) is a carboxylic-acid-rich, bio-derived, water-soluble, edible, hydrating, non-immunogenic polymer produced naturally by several microorganisms. Here, we re-emphasise the ability of Bacillus subtilis natto to naturally produce γ-PGA on whole seaweed, as well as for the yields and chemical properties of the material to be affected by the presence of Mn(2+). Hyaluronic acid (HA) is an extracellular glycosaminoglycan which presents a high concentration of carboxylic acid and hydroxyl groups, being key in fulfilling numerous applications. Currently, there are strong environmental (solvent use), social (non-vegan extraction), and economic factors pushing for the biosynthesis of this material through prokaryotic microorganisms, which is not yet scalable or sustainable. Our study aimed to investigate an innovative raw material which can combine both superior hygroscopicity and UV protection to the cosmetic industry. Comparable hydration effect of commercially available γ-PGA to conventional moisturising agents (HA and glycerol) was observed; however, greater hydration capacity was observed from seaweed-derived γ-PGA. Herewith, successful incorporation of seaweed-derived γ-PGA (0.2-2 w/v%) was achieved for several model cream systems with absorbances reported at 300 and 400 nm. All γ-PGA-based creams displayed shear thinning behaviour as the viscosity decreased, following increasing shear rates. Although the use of commercial γ-PGA within creams did not suggest a significant effect in rheological behaviour, this was confirmed to be a result of the similar molecular weight. Seaweed-derived γ-PGA cream systems did not display any negative effect on model HaCaT keratinocytes by means of in vitro MTT analysis.

Investigating the synergistic potential of Si and biochar to immobilize Ni in a Ni-contaminated calcareous soil after Zea mays L. cultivation

Abstract. In Iran, a significant percentage of agricultural soils are contaminated with a range of potentially toxic elements (PTEs), including Ni, which need to be remediated to prevent their entry into the food chain. Silicon (Si) is a beneficial plant element that has been shown to mitigate the effects of PTEs on crops. Biochar is a soil amendment that sequesters soil carbon and that can immobilize PTEs and enhance crop growth in soils. No previous studies have examined the potentially synergistic effect of Si and biochar on the Ni concentration in soil chemical fractions and the immobilization thereof. Therefore, the aim of this study was to examine the interactive effects of Si and biochar with respect to reducing Ni bioavailability and its corresponding uptake in corn (Zea Mays) in a calcareous soil. A 90 d factorial greenhouse study with corn was conducted. Si application levels were 0 (S0), 250 (S1), and 500 (S2) mg Si kg−1 soil, and biochar treatments (3wt %) including rice husk (RH) and sheep manure (SM) biochars produced at 300 and 500 °C (SM300, SM500, RH300, and RH500) were utilized. At harvest, the Ni concentration in corn shoots, the Ni content in soil chemical fractions, and the release kinetics of DPTA (diethylenetriaminepentaacetic acid)-extractable Ni were determined. Simultaneous utilization of Si and SM biochars led to a synergistic reduction (15 %–36 %) in the Ni content in the soluble and exchangeable fractions compared with the application of Si (5 %–9 %) and SM (5 %–7 %) biochars separately. The application of Si and biochars also decreased the DPTA-extractable Ni and Ni content in corn shoots (by up to 57 %), with the combined application of SM500 + S2 being the most effective. These effects were attributed to the transfer of Ni in soil from more bioavailable fractions to more stable iron-oxide-bound fractions, related to soil pH increase. SM500 was likely the most effective biochar due to its higher alkalinity and lower acidic functional group content which enhanced Ni sorption reactions with Si. The study demonstrates the synergistic potential of Si and SM biochar for immobilizing Ni in contaminated calcareous soils.

Enhanced Adsorption of Aqueous Pb(II) by Acidic Group-Modified Biochar Derived from Peanut Shells

Using peanut shells, a sustainable agricultural waste product, as its raw material, the acid group-modified biochar (AMBC) was prepared through phosphoric acid activation, partial carbonization, and concentrated sulfuric acid sulfonation for efficient removal of lead ion from aqueous solutions. Characterization techniques such as N2 isothermal adsorption–desorption, SEM, XRD, FT-IR, TG-DTA, and acid–base titration were utilized to fully understand the properties of the AMBC. It was found that there were high densities of acidic oxygen-containing functional groups (-SO3H, -COOH, Ph-OH) on the surface of the AMBC. The optimal adsorption performance of the AMBC for Pb(II) in water occurred when the initial concentration of Pb(II) was 100 mg/L, the pH was 5, the dosage of the adsorbent was 0.5 g/L, and the contact time was 120 min. Under the optimal conditions, the removal ratio of Pb(II) was 76.0%, with an adsorption capacity of 148.6 mg/g. This performance far surpassed that of its activated carbon precursor, which achieved a removal ratio of 39.7% and an adsorption capacity of 83.1 mg/g. The superior adsorption performance of AMBC can be caused by the high content of acidic oxygen-containing functional groups on its surface. These functional groups facilitate the strong binding between AMBC and Pb(II), enabling effective removal from water solutions.

STUDY OF NON-FUEL APPLICATION OF BROWN COAL DERIVATIVES IN THE PRODUCTION OF MEMBRANES BASED ON HYBRID BIODEGRADABLE MATERIALS

The article shows research into the non-fuel use of brown coal derivatives in the production of membranes based on hybrid biodegradable materials. The work used polylactide brand Terramac TP-4000, humic substances obtained from brown coals. Membranes for water purification from heavy metals were obtained from hybrid biopolymer materials based on pol- ylactide and humic substances in the form of polymer porous films with a pore size of 20 microns and a working surface area of the membrane of 28.26∙10-4 m2 with a circle diameter of 6 cm. Used in our The work of humic substances belonged to the group of well-hummified, more aromatic with a high content of acidic functional groups, which leads to their high com- plexing ability to form stable metal-humic complexes. The developed hybrid biodegradable materials based on polylactide and humic substances were used as highly effective sorption membrane materials to reduce the content of heavy metals in aqueous solutions. Obtaining membranes of hybrid biodegradable materials based on polylactide and humic substances have maximum selectivity for the extraction of metal ions in relation to Cu2+ – 95 % and Pb2+ – 94 %; and for metals such as Cd2+, Hg2+, Zn2+ and Co2+, it ranges from 82 to 89 %. Comparing the percentage of metal ions adsorbed, it can be seen that the easiest adsorbed metal was lead, copper and zinc adsorbed similarly, with cadmium showing the lowest percentage, but its adsorption was slightly worse than in the case of copper and zinc. The highest value was obtained for single adsorption of Cu2+ ions; in the case of adsorption from a mixture, this metal also had the highest distribution coefficient, and strong adsorption was also found for Pb2+. On the other hand, the adsorption of Zn2+ was, according to the “partition coefficient,” relatively weak. Strong and residual phases were highest for copper and lead, these two metals were largely bound into strong complexes by humic substances and only a very small amount could be washed out under normal conditions. It was found that the leaching of metal ions from mem- brane hybrid biodegradable materials based on polylactide and humic substances into water was very low, in most cases it was about 10 % and did not exceed 20 %. Most of the metal ions (≥60 %) were very tightly bound and were partially leached out under strongly acidic conditions. The obtained results of adsorption resistance vary significantly and correlate well with the age and degree of humification of humic substances.

Biomimetic cellulose membrane enables high-performance salinity gradient energy conversion: Coupling surface charge and nanopore structure

Surface charge and nanoscale porous structure of ion-selective membranes have been considered prominent in affecting conversion capability of salinity gradient energy-to-power, while the synergistic contribution of them is conventionally overlooked, thus limiting their further development toward high-performance harvesting of salinity gradient energy. Herein, bioinspired by organisms achieving effective intracellular ion transport through their surface-charged nanochannels, we designed porous-charged cellulose membrane (PCC) by simultaneously engineering surface charge and pore structure, followed by desirably chemical and structural distinctions, such as high zeta potential and sulfonic acid group content of −44 mV and 1.22 mmol/g, large porosity of 84 % and pore volume of 0.01 cm3/g (d ≤ 10 nm), while just −23 mV, 42 %, 0.0036 cm3/g and 0 mmol/g for pristine cellulose. Such distinctions endow PCC with excellent ion transport rate and capability (high t+ of 0.97 and η of 44.18 % in 0.001/0.01 M), correspondingly superhigh power density of 21.6 W/m2 (0.01/5 M), which surpasses that of most membrane materials, including biomass materials, synthesized polymers, and even some composite materials. By a tandem 30 PCC units, the output voltage of the designed PCC device reaches 2.24 V, which successfully powers calculator and light-emitting diode. In addition, our PCC demonstrates excellent stability in various pH system (from 3 to 11) during 30-day testing. The PCC with environmentally friendly, low cost, and large-scale advantages demonstrates strong competitiveness in advanced membrane materials toward high-performance manipulating ion transport.

The Effect of Macromonomer Surfactant Microstructure on Aqueous Polymer Dispersion and Derived Polymer Film Properties.

Water-borne coatings were prepared from poly(methyl methacrylate-co-butyl acrylate) latexes using different methacrylic acid containing macromonomers as stabilizers, and their physical properties were determined. The amphiphilic methacrylic acid macromonomers containing methyl, butyl, or lauryl methacrylate as hydrophobic comonomers were synthesized via catalytic chain transfer polymerization to give stabilizers with varying architecture, composition, and molar mass. A range of latexes of virtually the same composition was prepared by keeping the content of methacrylic acid groups during the emulsion polymerization constant and by only varying the microstructure of the macromonomers. These latexes displayed a range of rheological behaviors: from highly viscous and shear thinning to low viscous and Newtonian. The contact angles of the resulting coatings ranged from very hydrophilic (<10°) to almost hydrophobic (88°), and differences in hardness, roughness, and water vapor sorption and permeability were found.

Effect of Different Wheat Sprouting Conditions on the Characteristics of Whole-Wheat Flour.

Controlled sprouting promotes physiological and biochemical changes in whole grains, improves their nutritional value and offers technological advantages for breadmaking as an alternative to traditional whole grains. The aim of this study is to find sprouting conditions for the grains of Klein Valor wheat variety (Triticum aestivum L.) that would increase the nutritional value without significantly affecting the gluten proteins, which are essential in wholegrain baked goods. The chemical and nutritional composition, enzymatic activity and pasting properties of the suspensions of unsprouted and sprouted whole-wheat flour were evaluated. This bioprocess allowed us to obtain sprouted whole-wheat flour with different degrees of modification in its chemical composition. Sprouting at 25 °C resulted in an observable increase in enzymatic activity and metabolic processes, particularly α-amylases, which significantly affect the starch matrix and the associated pasting properties. Additionally, there was a smaller but still notable effect on the structure of the cell walls and the protein matrix due to the activation of endoxylanases and proteases. In contrast, sprouting at 15 and 20 °C for 24 h allowed for better process control as it resulted in nutritional improvements such as a higher content of free amino acid groups, free phenolic compounds and antioxidant capacity, as well as a lower content of phytates. In addition, it provided techno-functional advantages due to the moderate activation of α-amylase and xylanase. A moderate decrease in peak viscosity of sprouted whole-wheat flour suspensions was observed compared to the control flour, while protein degradation was not significantly prolonged. Sprouted whole-wheat flour obtained under milder sprouting conditions with moderate enzymatic activity could be a promising and interesting ingredient for wholegrain baked goods with improved nutritional values and techno-functional properties. This approach could avoid the use of conventional flour improvers and thus have a positive impact on consumer acceptance and enable the labelling of the product with a clean label.

Highly selective removal of thorium from acidic solutions achieved on phosphonic acid functionalized core–shell magnetic nanocomposite: Understanding adsorption and binding mechanisms

Thorium has received widespread attention as potential nuclear fuel alternative for the next-generation thorium-based molten salt reactors. With the growth of nuclear energy, it is needful to exploit magnetic nanomaterials to remove thorium from aqueous solutions, owing to their superparamagnetism and large specific surface energy. Nevertheless, most of magnetic nanomaterials often suffered from low thorium selectivity and poor structural ability in acidic solutions. Herein, a novel core–shell magnetic nanocomposite Fe3O4@SiO2/P (AA-MMA-VPA) possessing phosphonic acid was developed by a controlled radical polymerization of vinylphosphonic acid (VPA) in the presence of Fe3O4 encapsulated by SiO2 (Fe3O4@SiO2). Due to the presence of the high content of phosphonic acid groups and the absence of any universal groups, Fe3O4@SiO2/P (AA-MMA-VPA) displayed exceptional selectivity for thorium in the presence of 11 co-existing cations. The separation factor STh/M value for Fe3O4@SiO2/P(AA-MMA-VPA) concerning all other competing cations surpassed 74.4, and the largest value for STh/M even amounted to 343.5. Further, Fe3O4@SiO2/P (AA-MMA-VPA) possessed a maximum adsorption capacity (qmax) of 485.4 mg g−1 at pH of 3.0, higher than that of other magnetic sorbents. By reason of its core–shell structure, the sorbent possessed an outstanding structure stability even after immersed into HNO3 solution at pH of 0.5 for 72 h. The sorbent could as well be magnetically recouped, and recycled at least six times without evident diminution in sorption amount. The sterling removal performance of the sorbent was assigned to the interaction of thorium with phosphonic acid, corroborated by FT-IR, XPS and DFT method. Thus, this study affords a new viewpoint for exploiting magnetic nanomaterials with sterling acidic resistance for the strongly selective entrapment of thorium from acidic media.

Removal of antibiotics, bacterial toxicity, and occurrence of antibiotic resistance genes in secondary hospital effluents treated with granular activated carbon and the impact of preceding chlorination

This comprehensive investigation highlighted the complex adsorption behaviors of antibiotics onto granular activated carbon (GAC), the effectiveness of this adsorption in reducing bacterial toxicity, and the reduction of antibiotic resistance genes (ARGs) and antibiotic resistant bacteria (ARB) in hospital wastewater (HWW) effluents. Six GACs were characterized for their physicochemical properties, and their ability to adsorb six antibiotics in the background matrix of actual HWW was evaluated. Coconut shell-derived GAC (Co-U), which had the highest hydrophobicity and lowest content of oxygen-containing acidic functional groups, demonstrated the highest adsorption capacities for the tested antibiotics. Bacterial toxicity tests revealed that GACs could eliminate the bacterial toxicity from antibiotic intermediates present in chlorinated HWW. By contrast, the bacterial toxicity could not be removed by GACs in non-chlorinated HWW due to the greater presence of intermediate components identified by LC-MS/MS. The intraparticle diffusion coefficient of antibiotics adsorbed onto Co-U could be calculated by adsorption kinetics derived from the linear driving force model and the homogenous intraparticle diffusion model associated with the linear adsorption isotherms (0–150 μg/L). Meropenem and sulfamethoxazole exhibited the highest adsorption capacities in a single-solute solution compared to penicillin G, ampicillin, cetazidime, and ciprofloxacin. However, the greater adsorption capacities of meropenem and sulfamethoxazole disappeared in mixed-solute solutions, indicating the lowest adsorption competition. GAC can eliminate most ARGs while also promoting the growth of some ARB. Chlorination (free chlorine residues at 0.5 mg Cl2/L) did not significantly affect the overall composition of ARGs and ARB in HWW. However, the accumulation of ARGs and ARB on GAC in fixed bed columns was lower in chlorinated HWW than in non-chlorinated HWW due to an increase in the adsorption of intermediates.

Introducing sulfonic acid polymers into MOF nanochannels for ultra-high Ba2+ adsorption capacity and proton conductivity

Porous materials with a high concentration of sulfonic acid groups are highly desirable for applications such as radioactive Ba2+ adsorption, catalysis, and proton-conductive materials, but they are also challenging to synthesize. In this work, we introduce polymers containing sulfonic acid groups into the nanochannels of metal–organic frameworks (MOFs) through in-situ synthesis to enhance the sulfonic acid content. We use a alkene with sulfonic acid groups (2)-acrylamido-2-methylpropane sulfonic acid, AMPS) and a crosslinking agent N,N’-methylenebisacrylamide (MBAA) to synthesize two MOF composites, PAMPS@MIL-101 and PAMPS@MIL-101-SO3H, in the ultra-stable MIL-101 series through in-situ polymerization with free radical initiators. The two MOF composites have a high and uniform distribution of sulfonic acid groups in the MOF framework, which results in ultra-high barium ion adsorption capacity. The maximum adsorption amounts are 142.7 and 356.9 mg·g−1 for PAMPS@MIL-101 and PAMPS@MIL-101-SO3H, respectively, which are higher than those of most reported adsorbents. Importantly, the adsorption equilibrium can be achieved within 20 min. Moreover, both MOF composites, PAMPS@MIL-101 and PAMPS@MIL-101-SO3H, exhibit super proton conductivity, with values of 6.43 × 10−2 S·cm−1 and 1.43 × 10−1 S·cm−1 at 85 °C and 98 % RH, respectively. This method offers a new way of modifying MOF nanochannels with high sulfonic acid concentrations, and opens up new opportunities for developing radioactive Ba2+ adsorption materials and proton-conductive materials.

Interfacial Behavior and Long-Term Stability of the Emulsions Stabilized by Sugar Beet Pectin-Ca2+ Complexes with Different Cross-Linking Degrees.

Recent studies showed that sugar beet pectin exhibited more excellent emulsifying properties than traditional citrus peel pectin and apple pectin ascribed to the higher content of neutral sugar, protein, ferulic acid, and acetyl groups. It is precisely because of the extremely complex molecular structure of pectin that the emulsifying properties of the pectin-Ca2+ complex are still unclear. In this study, SBP-Ca2+ complexes with different cross-linking degrees were prepared. Subsequently, their interfacial adsorption kinetics, the resistance of interfacial films to external perturbances, and the long-term stability of the emulsions formed by these SBP-Ca2+ complexes were measured. The results indicated that the highly cross-linked SBP-Ca2+ complex exhibited slower interfacial adsorption kinetics than SBP alone. Moreover, compared with SBP alone, the oil-water interfacial film loaded by the highly cross-linked SBP-Ca2+ complex exhibited a lower elasticity and a poorer resistance to external perturbances. This resulted in a larger droplet size, a lower ζ-potential value, a larger continuous viscosity, and a worse long-term stability of the emulsion formed by the highly cross-linked SBP-Ca2+ complex. This study has very important guiding significance for deeply understanding the emulsification mechanism of the pectin-Ca2+ complex.

New approaches for regulation of structure and adsorption properties of biochar based on freshwater sediments (sapropels)

Biochar based on sapropel have been synthesized and the effect of chemical modification on their textural characteristics, acid-base and adsorption properties has been studied. It was found that preliminary treatment of raw sapropel with a weakly concentrated solution of alkali increases the fraction of micropores: from 0.006 cm3 g−1 (for BС-N) to 0.021 cm3 g−1 (for КОН-BC), and additional treatment with hydrofluoric acid leads to an increase in the fraction of micropores up 0.047 cm3 g−1 (for КОН-BC-HF) and also of specific surface area up to 211 m2 g−1 at a considerable decrease in the fraction of mineral part due to leaching of silicon-containing phases. The proposed chemical modification makes it possible not only to change the ratio of mineral and carbon parts and the pore space, but also to vary the surface properties of biochar: рНPZC, concentration and features of oxygen-containing groups. It is shown that the total content of acidic groups increases in the series BС-N (0.3290 mmol g−1) < КОН-BC (0.5567 mmol g−1) < КОН-BC-HF (1.3046 mmol g−1). Simultaneously the type of treatment affects the nature of oxygen-containing groups: the maximum amount of phenolic groups (0.4845 mmol g−1) in sample КОН-BC, the surface acidity of КОН-BC-HF is contented by the presence of a considerable amount of carboxyl groups (0.9198 mmol g−1). The analysis of the data obtained shows that the total content of acidic groups increases in the series The adsorption of Cu(II) ions from an aqueous solution on the synthesized samples of biochar was studied for the first time. Biochar obtained using the sapropel pretreated with alkali showed the maximum adsorption capacity toward copper ions of 27.9 mg g−1. Conceptual model identifying the mechanisms of adsorption copper (II) ions on biosorbent from sapropels was shown. The experimentally obtained isotherms were approximated using the Freundlich and Langmuir models. It was found that the adsorption of copper on the tested samples can be described quite adequately by the Langmuir monomolecular adsorption model (R2 ≥0.98).

Efficient Adsorption of Ammonia by Surface-Modified Activated Carbon Fiber Mesh.

In view of the characteristics and risks of ammonia, its removal is important for industrial production and environmental safety. In this study, viscose-based activated carbon fiber (ACF) was used as a substrate and chemically modified by nitric acid impregnation to enhance the adsorption capacity of the adsorbent for ammonia. A series of modified ACF-based adsorbents were prepared and characterized using BET, FTIR, XPS, and Boehm titration. Isotherm tests (293.15 K, 303.15 K, 313.15 K) and dynamic adsorption experiments were performed. The characterization results showed that impregnation with low concentrations of nitric acid not only increased the surface acidic functional group content but also increased the specific surface area, while impregnation with high concentrations of nitric acid could be able to decrease the specific surface area. ACF-N-6 significantly increased the surface functional group content without destroying the physical structure of the activated carbon fibers. The experimental results showed that the highest adsorption of ammonia by ACFs was 14.08 mmol-L-1 (ACF-N-6) at 293 K, and the adsorption capacity was increased by 165% compared with that of ACF-raw; by fitting the adsorption isotherm and calculating the equivalent heat of adsorption and thermodynamic parameters using the Langmuir-Freundlich model, the adsorption process could be found to exist simultaneously. Regarding physical adsorption and chemical adsorption, the results of the correlation analysis showed that the ammonia adsorption performance was strongly correlated with the carboxyl group content and positively correlated with the relative humidity (RH) of the inlet gas. This study contributes to the development of an efficient ammonia adsorption system with important applications in industrial production and environmental safety.

The relationship between chemical structure of perfluorinated sulfonic acid ionomers and their membrane properties for PEMEC application

Polymer electrolyte membrane electrolyzer cells (PEMECs) has been confirmed as a prototype electrochemical system that is effective in converting water into hydrogen and oxygen under the application of electricity. Among the core components of PEMEC, the polymer electrolyte membrane (PEM) determines critically an overall electrochemical performance of the PEMEC. Ideally a PEM system should exhibit a complex transport behavior of small molecules (e.g., gases and ions) while mediating flows of ions in the cell; it should exhibit high proton selectivity while serving as a gas barrier to hydrogen and oxygen to increase current efficiency, which are in turn vital factors in determining an effectiveness when the electric energy is used for water electrolysis. Until now, perfluorinated sulfonic acid (PFSA) ionomers have been extensively used as PEM materials in water electrolysis while in generating hydrogen and oxygen gases simultaneously in high purity. In this study we have examined the chemical structure of PEM membranes derived from various types of PFSA ionomers by employing solid-state 19F MAS NMR. Subsequently, a structure-property-performance correlation was sought in accordance with the chemical structure, the dispersion characteristics, and membrane properties of PFSA ionomers. Furthermore, the effects of the membrane morphology as well as the ionomer packing characteristics on proton conduction and hydrogen transportation were investigated. Lastly, the membrane properties exerted by varying the chemical architectures and equivalent weight (EW) values of PFSA ionomers in PEMEC were confirmed. 3 M 725 membrane, which has the highest concentration of sulfonic acid groups in the hydrated state, has the highest proton conductivity. In addition, it showed the best water electrolytic cell performance via the synergistic effect with low gas permeability obtained as a result from the short side chain structure.