Hydroxyl Content Research Articles

An insight on the role of Pr in the photocatalytic efficiency of mesoporous CeO2@C

Using Ce(NO3)3·6H2O and Pr(NO3)3·6H2O as raw materials, ammonium hydroxide as precipitate, acid red 14 (AR14) as carbon source, Ce-Pr-O@C was synthesized in this study. The structural properties of the resulted samples were characterized by XRD, N2 adsorption–desorption, Raman, TEM, UV–vis, FT-IR, and XPS techniques. The photocatalytic efficiency of Ce-Pr-O@C was evaluated by the degradation of AR14. Effect of Pr doping on the photocatalytic efficiency of Ce-Pr-O@C was focused on. The results show that 25% Pr doping amount is benefit for the formation of mesopores, improvement of hydroxyl group content, enhancement of bonding rate, resulting in the promotion of adsorption capacity of organic pollutants and separation of photogenerated electron and hole and thus increasing of photocatatlytic efficiency. Moreover, effect of carbon loading amount on the photocatatlytic efficiency was also investigated.

Exploring asphaltene aggregation: Model systems based on toluene-heptane mixtures

This work evaluates how chemical characteristics, such as polarity and aromaticity, can affect asphaltene aggregation. The asphaltene fraction was extracted from two different crude oils by precipitation in n-heptane, and these extracted asphaltenes were named A and B. Based on infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) analyses, we found that asphaltenes B present greater aromaticity. According to X-ray photoelectron spectroscopy (XPS), asphaltene B showed higher heteroatom content. Model systems based on toluene/n-heptane/asphaltene (0.05 g/L) were prepared to evaluate the aggregation/precipitation of asphaltenes. Dynamic light scattering (DLS) analysis of aggregation kinetics revealed that aromatic asphaltenes with higher heteroatom content tend to form larger aggregates. Moreover, hydroxyl content exhibits a greater impact on aggregation compared to diffusivity. Furthermore, once the aggregates reach a critical size, the suspension stability is reduced, and the aggregates sediment. The atomic force microscopy (AFM) and DLS results revealed a wide range of particle size distribution. The larger clusters likely consisted of smaller aggregates that adhered together. Still, we highlight that the sizes of these aggregates determined by AFM are not directly comparable to the measurements obtained from DLS. The drying of the samples for the AFM measurements probably affects the asphaltene aggregation process. For this reason, the results obtained from the AFM and DLS techniques are not comparable.

Investigation of bio-based rigid polyurethane foams synthesized with lignin and castor oil

In this study, polyurethane (PU) foams were manufactured using kraft lignin and castor oil as bio-based polyols by replacing 5–20 wt% and 10–100 wt% of conventional polyol, respectively. To investigate the effects of unmodified bio-based polyols on PU foam production, reactivity and morphology within PU composites was analyzed as well as mechanical and thermal properties of the resulting foams. Bio-based PU foam production was carried out after characterizing the reagents used in the foaming process (including hydroxyl group content, molecular weight distribution, and viscosity). To compare the resulting bio-based PU foams, control foam were produced without any bio-based polyol under the same experimental conditions. For lignin-incorporated PU foams, two types, LPU and lpu, were manufactured with index ratio of 1.01 and 1.3, respectively. The compressive strength of LPU foams increased with lignin content from 5 wt% (LPU5: 147 kPa) to 20 wt% (LPU20: 207 kPa), although it remained lower than that of the control foam (PU0: 326 kPa). Similarly, the compressive strength of lpu foams was lower than that of the control foam (pu0: 441 kPa), with values of 164 kPa (lpu5), 163 kPa (lpu10), 167 kPa (lpu15), and 147 kPa (lpu20). At 10 wt% lignin content, both foams (LPU10 and lpu10) exhibited the smallest and most homogenous pore sizes and structures. For castor oil-incorporated PU foams with an index of 1.01, denoted as CPU, increasing castor oil content resulted in larger cell sizes and void fractions, transitioning to an open-cell structure and decreasing the compressive strength of the foams from 284 kPa (CPU10) to 23 kPa (CPU100). Fourier transform infrared (FT-IR) results indicated the formation of characteristic urethane linkages in PU foams and confirmed that bio-based polyols were less reactive with isocyanate compared to traditional polyol. Thermogravimetric analysis (TGA) showed that incorporating lignin and castor oil affected the thermal decomposition behavior. The thermal stability of lignin-incorporated PU foams improved as the lignin content increased with char yields increasing from 11.5 wt% (LPU5) to 15.8 wt% (LPU20) and from 12.4 wt% (lpu5) to 17.5 wt% (lpu20). Conversely, the addition of castor oil resulted in decreased thermal stability, with char yields decreasing from 10.6 wt% (CPU10) to 4.2 wt% (CPU100). This research provides a comprehensive understanding of PU foams incorporating unmodified biomass-derived polyols (lignin and castor oil), suggesting their potential for value-added utilization as bio-based products.

Role of alumina particles in chemical-mechanical synergies in ruthenium polishing

Abrasive particles are usually considered to only play a "mechanical wear" role in the metal chemical mechanical polishing (CMP) process, neglecting their influence on chemical reactions. This study reveals the chemical role of Al2O3 particles in ruthenium (Ru) CMP by comparing the properties and polishing performance of Al2O3-SiO2 mixed slurry and pure SiO2 slurry. Several testing methods are used to investigate the mechanical and chemical actions of Al2O3 particles, including particle size distribution, Zeta potential, electrochemical reaction kinetics, oxide layer property and hydroxyl radical detection test. The results indicate that Al2O3 particles enhance the mechanical action by reducing the Zeta potential, and promote the chemical action by catalyzing hydrogen peroxide to produce hydroxyl radical (Fenton-like reaction) on Ru surface. These increase the material removal rate of Ru CMP with mixed slurry by nearly 5 times, while the surface roughness decreases by 60 %. The mechanism of chemical reaction promoted by increasing the hydroxyl radical concentration on Ru surface is confirmed from the aspects of increased corrosion current, oxide layer thickness and proportion of higher-valence Ru oxide (RuO2) in the oxide layer. Among them, the thickened oxide layer is a significant factor contributing to the substantial improvement in the material removal rate of Ru and the reduction in surface roughness. This study enhances the understanding of the chemical-mechanical synergistic mechanism of abrasive particles in metal polishing and elucidates the principle of this mechanism on promoting material removal and surface quality. It also provides new research ideas and theoretical guidance for efficient and high-quality metal polishing.

Green preparations of nanolignin from acid-saccharification-treated sugarcane trash

Characterization of isolated lignin and utilization of nanotechnology to produce nanolignin as a functional material are paramount. Lignin was extracted from acid-saccharification sugarcane trash (SCT-ASac) to produce acid-saccharification lignin (ASac-lignin). Then, lignin was further processed to nanolignin by a self-assembly dialysis process using THF:ethanol (1:1) as the solvent. The chemical, physical, and thermal properties of the lignin were evaluated, and the nanolignin size was confirmed via morphological analysis and PSA. SCT-ASac treatment prior to lignin isolation affects the structure of SCT and enhances the accessibility of lignin. Furthermore, this pretreatment can reduce residual carbohydrates, increasing the purity value. ASac-lignin has a nonconjugated phenolic group structure with a high number of β-O-4 bonds, a syringyl content, aromatic groups with low thermal stability, and a molecular weight with good phenolic hydroxyl content and total phenolic compounds. The obtained nanolignin is a spherical and more uniform particle with sizes less than 100 nm. ASac-nanolignin has the potential to be an environmentally friendly material in derivative lignin synthesis.

Production, thermal recycling, and application of cardanol-based polyurethane foam with phenol-carbamate bonds

The economic processing, sustainable recycling, and environmentally friendly application of polyurethane (PU) foams are important issues that need to be addressed urgently. In this study, we propose a strategy for the comprehensive utilization of cardanol and cashew shells to design cardanol-based PU (CPU) foams and wood-plastic films that can be recycled and reused. Firstly, cardanol-based polyphenols (CBPs) with a phenolic hydroxyl content of 3.29 mmol/g were prepared by Friedel-Crafts alkylation reaction using cardanol and guaiacol as raw materials. Subsequently, CPU foams were prepared by reacting CBPs with isocyanate, and the vertical and parallel compressive strengths could reach up to 0.27 MPa and 0.32 MPa, respectively, when the addition of CBPs was 80 %. These CPU foams, containing dynamic phenol-carbamate bonds, could be hot-pressed into transparent and smooth CPU films with tensile strengths of up to 30.5 MPa and could be re-formed at least three times. Finally, CPU foam and cashew shell waste were mixed and hot-pressed to produce a green wood-plastic composite with a tensile strength of up to 38.8 MPa. The resulting CPU-Wood films could be repaired or reshaped at least five times (38.0 MPa and 38.1 MPa) and could be formed into various shapes. This research paves the way for large-scale industrial production of recyclable and regenerative bio-based foams, making effective use of waste materials to achieve environmentally friendly production processes.

Parametric analysis on the apparent purity of Ni powder synthesized via hydrazine-reduction of aqueous NiSO4

The present research focuses on the synthesis of high-purity nickel powder through solution-based chemical reduction using hydrazine hydrate as a reducing agent. A series of synthesis experiments were carried out with variations in the concentration ratio of hydrazine to nickel ions ([N2H4]/[Ni2+] = 5–15), the concentration ratio of hydroxyl ions to nickel ions ([OH−]/[Ni2+] = 10–20), temperature (T = 60–80 °C), and reaction time (t = 30–90 min). The Taguchi L9 design of experiments and analysis of variance (ANOVA) was used to identify the role of the hydroxyl-to-nickel ion ratio ([OH⁻]/[Ni2⁺]) in determining the apparent purity of the nickel powder. The highest apparent nickel powder content, which was 92.75 %, was obtained in the experiment with [N2H4]/[Ni2+] = 5, [OH−]/[Ni2+] = 12.5, T = 60 °C, and t = 30 min. The optimum conditions that significantly influence the apparent purity of nickel powder derived from data processing are used as the basis for the second stage of the experiment to determine the effect of the [OH−]/[Ni2+] ratio on particle size, morphology, and purity of the synthesized nickel powder. It was found that higher hydroxyl concentrations lead to finer particles, and the morphology of nickel particles is linked to their apparent purity, with the chain of beads of nanoparticle aggregates morphology achievable when [OH−]/[Ni2+] = 12.5 and [OH−]/[Ni2+] = 15. The presented results may contribute to filling the gap in the knowledge to synthesize high-purity nickel powder with controlled size and morphology, which can be used in various applications such as catalysts, conductive fillers, and advanced electrodes.

Self-heating photothermal synergistic catalytic decomposition of carcinogenic formaldehyde by α-MnO2 at ambient temperature: Functional roles of surface acidic-basic sites

Formaldehyde is a major pollutant in indoor atmosphere, and the realization of complete mineralization of formaldehyde at room temperature is of great significance and practical demand for improving indoor air quality. Surface acidic-basic sites, as one of the important surface properties that have significant influence on catalytic oxidation of formaldehyde, revealing their functions is beneficial for the development of efficient formaldehyde decomposition materials. Herein, the α-MnO2 acidic-basic sites were regulated and its effects on self-heating photothermal catalytic oxidation of formaldehyde were further contrastive investigated. The acidic-basic sites showed distinct functions: the basic sites exhibited a significant promotion on formaldehyde oxidation; While the acidic sites greatly inhibited the reactivity. Particularly, the basicity enhanced α-MnO2 could reach the 100% conversion of formaldehyde at ambient temperature. Furthermore, the self-heating photothermal mechanism was consonant with the thermal-assisted photocatalysis mechanism, rather than traditional photo-drive thermal catalysis mechanism. The strength of basic sites significantly increased the content of surface hydroxyl groups, and the electron-rich basic sites were favorable for the activation of oxygen, thereby generating more reactive oxygen species for the decomposition of formaldehyde. Moreover, in-situ DRIFTS reveals that the enhancement of basic sites can accelerate the rate oxidation of HCHO to generate formates and carbonates. This work clarified the influence of surface acid-base properties on formaldehyde photothermal decomposition.

Enhancing Surface Hydroxyl Group Modulation on Carbon Nitride Boosts the Effectiveness of Photodynamic Treatment for Brain Glioma.

The effectiveness of photodynamic therapy (PDT) in treating brain gliomas is limited by the solubility of photosensitizers and the production of reactive oxygen species (ROS), both of which are influenced by the concentration of photosensitizers and catalyst active sites. In this study, we developed a controllable surface hydroxyl concentration for the photosensitizer CN11 to address its poor water solubility issue and enhance PDT efficacy in tumor treatment. Compared to pure g-C3N4 (CN), CN11 exhibited 4.6 times higher hydrogen peroxide production under visible light, increased incidence of the n → π* electron transition, and provided more available reaction sites for cytotoxic ROS generation. These findings resulted in a 2.43-fold increase in photodynamic treatment efficacy against brain glioma cells. Furthermore, in vivo experiments conducted on mice demonstrated that CN11 could be excreted through normal cell metabolism with low cytotoxicity and high biosafety, effectively achieving complete eradication of tumor cells.

From theory to application: Innovative ice-phobic polyurethane coatings by studying material parameters, mechanical insights, and additives

This investigation introduces new insights into the influence of material parameters on the anti-icing properties of polyurethane (PU) coatings, encompassing chemical characteristics, cross-link densities, mechanical analysis, and additive diversity. To comprehensively address these aspects, a meticulous exploration was conducted to delve into the effects of these parameters on wettability and icephobicity. To fabricate the PU coatings, three distinct acrylic polyols with various hydroxyl content along with two widely employed aliphatic isocyanates boasting diverse %NCO values were utilized. By employing stoichiometric and non-stoichiometric ratios, an array of coatings with different crosslink densities and mechanical properties was fabricated. The principal influence of crosslink density alterations in PU coatings on ice nucleation temperature and ice adhesion strength emerged distinctly, underpinned by the establishment of hydrogen bonds between water molecules and polar functional groups within the coating, coupled with the appearance of a quasi-liquid layer (QLL). The mechanical properties, wettability characteristics, and surface roughness of the coatings were examined and it was clearly demonstrated that Young's modulus and physicochemical properties play significant roles in the characteristics of ice adhesion strength. In particular, lower Young's modulus in the samples was associated with reduced ice adhesion, albeit with compromised durability. In the next step of this investigation, the matrix demonstrating optimal mechanical properties and icephobicity was subjected to surface energy adjustment. This was accomplished by introducing various concentrations of both fluorinated and non-fluorinated additives. This adjustment led to a significant reduction of ice adhesion strength, measuring less than 100 Kpa as an icephobic PU coating. Nevertheless, it was observed that the effectiveness of the fluorinated additives diminished after repetitive icing-deicing cycles, while the non-fluorinated additive maintained its influence on ice adhesion strength even after numerous cycles. The interplay between material attributes, mechanical properties, and additive influences has been meticulously unraveled, charting a course for further advancements in the pursuit of robust icephobic coating.

EDTA functionalized pine needle biochar (EDTA@BC); a valorized bio-material for removal of Ni(II) from aqueous solution.

The preparation of ethylenediaminetetraacetic acid (EDTA) functionalized pine needles biochar (EDTA@BC) as a low-cost active adsorbent and its effectiveness in removing Ni(II) from aqueous solution at various conditions is reported in this paper. First, alkali activation was selected to render the pine needle biochar with an excellent porous structure and increased concentration of hydroxyl groups to facilitate grafting. Subsequently, a simple method was utilized to graft EDTA onto the biochar. The prepared EDTA@BC was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy dispersive x-ray spectrometry (EDX). Batch adsorption studies were conducted to assess the impact of various parameters such as solution pH, adsorbent dosage, adsorbate volume, and shaking time on the removal efficiency of Ni(II). At pH 6, 100 mg dosage, 4 mL of adsorbate volume, and 10 min of shaking time, the maximum removal efficiency of Ni(II) was observed to be 89%. EDTA@BC showed reasonable sorption performance still after the third cycle of regeneration. The effect of interfering ions such as Pb, Cr, Cu, and Hg was evaluated, resulting a decrease of 69%, 78%, 76%, and 68%, respectively, in its sorption capacity. The Langmuir model provided a better fit for Ni(II) in the concentration range of 0.1-2000 ppm under optimized conditions, with qmax of 46.69 ± 1.031 mg/g and KL of 0.001, compared with the Freundlich isotherm, which yielded n = 0.234 and χ2 = 2.7899, Temkin isotherm (R2 = 0.9520), and Redlich-Peterson isotherm (R2 = 0.9725). The removal of Ni(II) by EDTA@BC was found to be the pseudo-second-order kinetics. Thermodynamic studies indicated adsorption process to be endothermic and nonspontaneous. Hence, a sustainable valorized bio-material (EDTA@BC) is prepared having better sorption efficiency of Ni(II) from aqueous solution with possible wide applicability. RESEARCH HIGHLIGHTS: New EDTA functionalized indigenous pine needles biochar (EDTA@BC) was prepared. This low-cost active adsorbent found effective in removing Ni(II) from aqueous solution. FTIR, SEM, and EDX proved synthesis and uptake of Ni(II) from aqueous solution. Ni(II) removal, regeneration, interfering and adsorption studies were performed by UV-Vis spectroscopy.

Preparation of high antioxidant nanolignin and its application in cosmetics

Lignin, as a natural polyphenol, displays anti-oxidant activity by trapping and binding free radicals through its free phenolic hydroxyl groups. However, the most accessible form, industrial lignins, generally has low phenolic hydroxyl content, which severely limits their application value and scenarios. Herein, we showed that potassium-glycerate deep eutectic solvent (PG-DES) treatment can be combined with laccase oxidation to afford prepared high antioxidant lignin nanoparticles (HA-LNPs) with notably improved anti-oxidant activities benefiting from both the enhanced phenolic hydroxyl content 170.8 % and reduced average particle size (59.0 nm). At concentrations as low as 60 μg/mL, HA-LNPs showed favorable effects in promoting collagen formation. When HA-LNPs were used as an active ingredient in the anti-aging mask formulation, the reactive oxygen species (ROS) scavenging activity of mask samples containing 0.4 % HA-LNPs reached 37.2 %. The data suggest great promise of HA-LNPs as a natural antioxidant for formulating in anti-aging skin care products.

Spatial atomic layer deposition of nitrogen-doped alumina thin films for high-performance perovskite solar cell encapsulation

An atmospheric-pressure spatial atomic layer deposition (AP-SALD) system is used to deposit nitrogen-doped alumina (N-AlOx) thin-film-encapsulation layers. The rapid nature of the AP-SALD process facilitates deposition of 60-nm layers directly on perovskite solar cells at 130 °C with no damage to the temperature-sensitive perovskite and organic materials. Varying the bubbling of a NH4OH precursor varied the nitrogen concentration from 0.08 to 0.68 at%. These small concentrations were found to have a significant impact on the structural properties of the films and their moisture barrier performance. The N-AlOx thin films had slightly higher growth rates than undoped AlOx, less unwanted hydroxyl and carbon content, and were smoother and more compact, which was attributed to a higher flux of reactive species from the volatile NH4OH. Optical calcium tests showed that the N-AlOx films had lower water-vapor-transmission rates (∼10-5 g/m2/day) than undoped AlOx films and the transmission was minimized for 0.28% nitrogen. The increased compactness of the N-AlOx films is expected to minimize nanoscale percolation pathways, whereas higher nitrogen-defect concentrations may facilitate water permeation through these pathways. The stability of n-i-p and p-i-n perovskite solar cells under standard ISOS-D-1 and ISOS-D-3 testing conditions was significantly enhanced by the encapsulation layers. An N-AlOx encapsulation layer with 0.28% nitrogen improved the T80 value of a p-i-n formamidinium methylammonium lead iodide solar cell from 144 hrs to 855 hrs (ISOS-D-1) and 52 hrs to 300 hrs (ISOS-D-3).

Unlocking the potential of phenolated kraft lignin as a versatile feed additive

Lignin, a renewable natural antioxidant and bacteriostat, holds promise as a versatile, cost-effective feed additive. However, traditional industrial lignin faces limitations, including low reactivity, poor uniformity, and unstable properties, necessitating chemical modification. Complex modification methods pose economic and toxicity challenges, so this study adopted a relatively simple alkali-catalyzed phenolization approach, using phenol, catechol, and pyrogallol to modify kraft lignin, and characterized the resulting products using various techniques. Subsequently, their antioxidant, antibacterial, adsorption properties for heavy metal ions and mycotoxins, growth-promoting properties, and antiviral abilities were assessed. The phenolation process led to lignin depolymerization and a notable increase in phenolic hydroxyl content, particularly in pyrogallol-phenolated lignin (Py-L), rising from 3.08 to 4.68 mmol/g. These modified lignins exhibited enhanced antioxidant activity, with over 99 % inhibition against E. coli and S. aureus, and remarkable adsorption capacities for heavy metal ions and mycotoxins. Importantly, Py-L improved the growth performance of mice and reduced influenza mortality. Furthermore, density functional theory calculations elucidated the mechanism behind the enhanced antioxidant properties. This study presents a promising avenue for developing versatile feed additives to address challenges related to animal feed antioxidant supplementation, bacterial control, and growth promotion.

Enhanced interfacial, mechanical, and anti-hygrothermal properties of carbon fiber/cyanate ester composites with the catalytic sizing agents of titanium epoxy

The mechanical properties of composites are closely related to the interfacial behavior, especially under the hygrothermal circumstance. A catalytic sizing agent of titanium epoxy is designed to enhance interfacial, mechanical, and anti-hygrothermal properties of high modulus carbon fiber (HMCF)/cyanate ester composites simultaneously. The mechanisms of interface enhancement and low hygroscopicity of composites are investigated. The titanium epoxy is synthesized and its catalytic effect on the curing of cyanate ester is proved. The interfacial properties of HMCF composites with catalytic sizing agents are improved to 95.5 MPa, which is attributed to the interphase with high crosslinking density and sufficient triazine rings and oxazolidinone structure due to preferential curing induced by interfacial catalysis, stimulating the smooth transition of interphase modulus. Further, the formed interphase exhibits few interface defects and low content of hydroxyl groups, which changes the moisture diffusion path and reduces saturated water absorption of composites to only 0.36 %, resulting in the release of interfacial wet stress concentration and high retention of mechanical properties in hygrothermal environment. The resultant composites with high stiffness, excellent temperature resistance, superior dimensional stability and low moisture absorption are expected to be applied to high-orbit space, aerospace, precision instruments.

Capture of single Ag atoms through high-temperature-induced crystal plane reconstruction

The “terminal hydroxyl group anchoring mechanism” has been studied on metal oxides (Al2O3, CeO2) as well as a variety of noble and transition metals (Ag, Pt, Pd, Cu, Ni, Fe, Mn, and Co) in a number of generalized studies, but there is still a gap in how to regulate the content of terminal hydroxyl groups to influence the dispersion of the active species and thus to achieve optimal catalytic performance. Herein, we utilized AlOOH as a precursor for γ-Al2O3 and induced the transformation of the exposed crystal face of γ-Al2O3 from (110) to (100) by controlling the calcination temperature to generate more terminal hydroxyl groups to anchor Ag species. Experimental results combined with AIMD and DFT show that temperature can drive the atomic rearrangement on the (110) crystal face, thereby forming a structure similar to the atomic arrangement of the (100) crystal face. This resulted in the formation of more terminal hydroxyl groups during the high-temperature calcination of the support (Al-900), which can capture Ag species to form single-atom dispersions, and ultimately develop a stable and efficient single-atom Ag-based catalyst.

In situ acid production by organic matter induced with trace homogeneous Fenton reagent for membrane fouling control

The homogeneous Fenton process involves both coagulation and oxidation, but it requires added acidity, so it is rarely used to control membrane fouling. This work found that the pH of neutral simulated wastewater sharply declined to 4.1 after pre-treatment with 0.1 mM Fenton reagent (Fe2+:H2O2=1:1) without added acidity. This occurred mainly because the trace homogeneous Fenton reagent induced in situ acid production by organic matter in the wastewater, which supplied the acidic conditions required for the Fenton reaction and ensured that the reaction could proceed continuously. Then, oxidation during the pre-Fenton process enhanced the electrostatic repulsion forces and effectively weakened the hydrogen bonds of organic matter at the membrane surface by altering the net charge and hydroxyl content of organic matter, while coagulation caused the foulants to gather and form large aggregates. These changes diminished the deposition of foulants onto the membrane surface and resulted in a looser fouling layer, which eventually caused the membrane fouling rate to decline from 83 % to 24 % and the flux recovery rate to increase from 44 % to 98 % during 2 h of filtration. This membrane fouling mitigation ability is much superior to that of pre-H2O2, pre-Fe2+ or pre-Fe3+ processes with equivalent doses.

Effects of pH-varying thermal modification on sewage sludge: A focus on releasing nitrogen- and phosphorus-containing substances

Sewage sludge is promising for the recovery and utilisation of nutrient components, but its complex nature hinders the release of these components. The combination of pH and thermal modifications shows promise for the release of nutrient components from sludge. However, comprehensive studies on the full spectrum of pH levels and corresponding mechanisms of pH-varying thermal modification are lacking. In this study, the main nutrient components, physicochemical properties, molecular structure, and noncovalent interactions of sludge were comprehensively investigated through pH-varying thermal modification (within a pH range of 2.0 to 12.0 under the same thermal condition). The experimental results showed that the release of main organics, particularly nitrogen (N)-containing organics, was well-fitted, with a tick-like function (R2: 0.74–0.96). The thermal protons exhibited a notable accumulative mutagenic effect on the N-containing organics release, while the thermal hydroxyl ions had a more direct effect, as revealed by the changes in multivalent metals and molecular structures with the protonation–deprotonation of carboxyl groups. The driving force for the release of N-containing organics was identified as the fluctuation of electrostatic interactions at the solid–liquid interface of the sludge. However, the release of phosphorus (P)-containing substances exhibited a contrasting response to that of N-containing substances with varying pH, likely because the reaction sites of thermal protons and thermal hydroxyl ions for P-containing substances were different. Moreover, high concentrations of thermal protons and hydroxyl ions collapsed the Lifshitz–van der Waals interactions of sludge, resulting in a decrease in viscoelasticity and binding strength. These propositions were further confirmed through statistical analyses of the main indicators of the main nutrient components, physicochemical properties, and noncovalent interactions of sludge. These findings can provide a basis for optimising characteristic-specific methods to recovery nutrient components (N/P) from sludge.

Multi-site sulfonation of lignin for the synthesis of a high-performance dye dispersant

Sulfonated lignin-based dye dispersants have intensively attracted attention due to their low cost, renewability and abundant sources. However, their utilization is limited by the low content of sulfonic groups and high content of hydroxyl groups in their complex lignin structure, which results in various problems such as high reducing rate of dye, severe staining of the fibers and uneven dyeing. Here, the multi-site sulfonated lignin-based dispersants were prepared with high sulfonic group content (2.20 mmol/g) and low hydroxyl content (2.43 mmol/g). When using it as the dispersant, the dye uptake rate was improved from 69.23 % to 98.55 %, the reducing rate was decreased from 20.82 % to 2.03 %, the K/S value was reduced from 0.69 to 0.02, and the particle sizes in dye system before and after high temperature treatment were stabilized below 0.5 μm. Besides, the dispersion effect was significantly improved because no obvious separation between dye and water was observed even if without the assistance of grinding process. In short, the multi-site sulfonation method proposed in this work could remarkably improve the performances of the lignin-based dye dispersants, which would facilitate the development of the dye dispersion and the high value utilization of lignin.

Higher efficiency of vanadate iron in heterogeneous Fenton-like systems to pretreat sugarcane bagasse and its enzymatic saccharification.

Pretreatment is crucial for effective enzymatic saccharification of lignocellulose such as sugarcane bagasse (SCB). In the present study, SCB was pretreated with five kinds of heterogeneous Fenton-like systems (HFSs), respectively, in which α-FeOOH, α-Fe2O3, Fe3O4, and FeS2 worked as four traditional heterogeneous Fenton-like catalysts (HFCs), while FeVO4 worked as a novel HFC. The enzymatic reducing sugar conversion rate was then compared among SCB after different heterogeneous Fenton-like pretreatments (HFPs), and the optimal HFS and pretreatment conditions were determined. The mechanism underlying the difference in saccharification efficiency was elucidated by analyzing the composition and morphology of SCB. Moreover, the ion dissolution characteristics, variation of pH and Eh values, H2O2 and hydroxyl radical (·OH) concentration of FeVO4 and α-Fe2O3 HFSs were compared. The results revealed that the sugar conversion rate of SCB pretreated with FeVO4 HFS reached up to 58.25%, which was obviously higher than that under other HFPs. In addition, the surface morphology and composition of the pretreated SCB with FeVO4 HFS were more conducive to enzymatic saccharification. Compared with α-Fe2O3, FeVO4 could utilize H2O2 more efficiently, since the dissolved Fe3+ and V5+ can both react with H2O2 to produce more ·OH, resulting in a higher hemicellulose and lignin removal rate and a higher enzymatic sugar conversion rate. It can be concluded that FeVO4 HFP is a promising approach for lignocellulose pretreatment.