Adsorption-photocatalysis synergy of reusable mesoporous TiO2-ZnO for photocatalytic degradation of doxycycline antibiotic.

The potentials of mesoporous TiO2-ZnO (3TiZn) were explored on photocatalytic degradation of doxycycline (DOX) antibiotic, likewise the influence of adsorption on the photocatalytic process. The 3TiZn was characterized for physical and chemical properties. Stability, reusability, kinetic and the ability of 3TiZn to degrade high concentration of pollutant under different operating conditions were investigated. Photocatalytic degradation of DOX was conducted at varied operating conditions, and the best was obtained at 1 g/L catalyst dosage, solution inherent pH (4.4) and 50 ppm of DOX. Complete degradation of 50 ppm and 100 ppm of DOX were attained within 30 and 100 min of the reaction time, respectively. The stability and reusability study of the photocatalyst proved that at the tenth (10th) cycle, the 3TiZn is as effective in the degradation of DOX as in the first cycle. This may be attributed to the fusion of the mixed oxides during calcination. The 3TiZn is mesoporous with a pore diameter of 17 nm, and this boosts it potential to degrade high concentration of DOX. It was observed that the adsorption capacity of 3TiZn enhance the photocatalytic process. It can be emphasized that 3TiZn portrayed a remarkable catalyst stability and good potentials for industrial application.

Cross-linked chitosan-epichlorohydrin/bentonite composite for reactive orange 16 dye removal: Experimental study and molecular dynamic simulation.

Chitosan/bentonite beads (CsB) composites were prepared from chitosan (Cs) and bentonite (B) and cross-linked with epichlorohydrin for removal of reactive orange 16 (RO16) and methylene blue (MB). The adsorption results have shown that the (Cs20B80), 20 % wt of (Cs) and 80 % (B), was selected as the best adsorbent for (MB) and (RO16) dyes. SEM, EDX, FTIR, BET, and pHpzc were implemented to investigate the features of Cs, B, and Cs20B80 samples. The influence of contact time (0-72 h), initial RO16 concentration (15-300 mg/L), temperature (30, 40, and 50 °C), the quantity of adsorbent (1-4 g/L), ion strength (0.1-1 M), and solution pH (3-10) on RO16 adsorption onto Cs20B80 were explored. The pseudo-second-order and the Langmuir models fit adequately the adsorption kinetic results and the isotherms ones respectively. Also, the maximal monolayer capacities calculated using the non-linear form of the Langmuir isotherm are 55.27, 55.29, and 70.80 mg/g, at 30, 40 and 50 °C. Based to the statistical physics model, the RO16 could be retained on the surface of Cs20B80 through a non-parallel orientation. The RO16 adsorption process is endothermic and natural, as demonstrated by thermodynamic studies. After three regeneration cycles, the Cs20B80 composite has shown an adsorption capacity of around 20 % compared to the initial one. The adsorption energy of RO16 onto Cs, B, and Cs20B80 examined using the Monte Carlo simulation method (MC) ranged from -164.8 to -303.7 (kcal/mol), showing the potential of the three adsorbants for RO16 dye. Also, the process of adsorption of RO16 dye on the surface of Cs20B80 composite indicates several kinds of physical interactions, involving electrostatic interaction, hydrogen bonding, and π-π interactions, this finding was proved theoretically via molecular dynamic simulations.

The Preoperative Serum Levels of the Anaphylatoxins C3a and C5a and Their Association with Clinico-Pathological Factors in Breast Cancer Patients.

Breast cancer is a common women malignancy worldwide. Emerging evidence suggests that various complement molecules function as an immune suppressors in the tumor microenvironment (TME). Therefore this study aimed to investigate the role of the anaphylatoxins C3a and C5a in the propagation of breast cancer and their relationships with clinicopathological factors in Iraqi women suffering from breast tumors. ELISA technique was used to determine the serum anaphylatoxins C3a and C4a levels in 60 Iraqi women with breast tumors (30 with primary breast cancer and 30 with benign breast tumor) before surgery and treatment as 30 healthy controls. In addition, the clinicopathological factors of all the patients were collected. The result showed a significantly increased level of anaphylatoxins C3a and C5a (P<0.001) in primary breast cancer patients than in benign breast tumor and healthy control women. The area under the curve (AUC) of C3a and C5a for distinguishing patients with primary breast cancer and healthy control subjects was 0.878 (95% CI: 0.768 to 0.948) and 0.953 (95% CI: 0.865 to 0.991) respectively. C5a correlated with larger tumor size, lymph node metastasis, and histologic grade III, whereas C3a only with lymph node metastasis. In conclusion, preoperative levels of C5a exhibit high accuracy for primary breast cancer than C3a. C5a correlated with tumor burden more than C3a and suggested an enhancing effect of C5a on BC proliferation. Thus, suggesting prognostic value for C5a in primary BC.

Chitosan-derived hydrothermally carbonized materials and its applications: A review of recent literature.

Chitosan (CS) is a linear polysaccharide biopolymer, one of the most abundant biowastes in the environment. This makes chitosan a potential material for a wide range of applications. To improve CS's properties, chitosan has to be chemically modified. Hydrothermal carbonization (HTC) is a sustainable process for converting chitosan to solid carbonized material. This article presents a review on the applications of hydrothermally treated chitosan in different fields such as water treatment, heavy metals adsorption, carbon dioxide capturing, solar cells, energy storage, biosensing, supercapacitors, and catalysis. Moreover, this review covers the impact of HTC process parameters on the properties of the produced carbon material. The diversity of applications indicates the great possibilities and multifunctionality of hydrothermally carbonized chitosan and its derivatives. The utilization of HTC-CS is expected to further expand as a result of the movement toward sustainable, environmentally-friendly resources. Thus, this review also recommends a few suggestions to improve the properties of HTC chitosan and its comprehensive applications.

Review on recent progress in chitosan/chitin-carbonaceous material composites for the adsorption of water pollutants.

Chitosan and chitin are categorized as low cost, renewable and eco-friendly biopolymers. However, they have low mechanical properties and unfavorable pore properties in terms of low surface area and total pore volume that limit their adsorption application. Many studies have shown that such weaknesses can be avoided by preparation of composites with carbonaceous materials from these biopolymers. This article provides a systematic review on the preparation of chitosan/chitin-carbonaceous material composites. Commonly used carbonaceous materials such as activated carbon, biochar, carbon nanotubes, graphene oxide and graphene to prepare composites are discussed. The application of chitosan/chitin-carbonaceous material composites for the adsorption of various water pollutants, and the regeneration and reusability of adsorbents are also included. Finally, the challenges and future prospects for the adsorbents applied for the adsorption of water pollutants are summarized.

Mesoporous biohybrid epichlorohydrin crosslinked chitosan/carbon-clay adsorbent for effective cationic and anionic dyes adsorption.

Epichlorohydrin crosslinked chitosan/carbon-clay (CSCC) biohybrid adsorbent was prepared for the adsorption of cationic methylene blue (MB) and anionic azo acid blue 29 (AB 29). The 40:60 wt% of chitosan (CS) and carbon-clay (CC) was selected as the best biohybrid adsorbent (CS40CC60) for the adsorption of both dyes. The adsorption of MB and AB 29 on CS40CC60 was carried out in a batch process to investigate the effects of initial dye concentration (25-400 mg/L), initial pH (3-11), contact time and adsorption temperature (30, 40 and 50 °C). The kinetics results of dyes adsorption onto CS40CC60 fit well to the pseudo-second-order model. The isotherms analysis demonstrated that the Freundlich isotherm described the adsorption data, and the qmax (mg/g) were 95.31 for MB and 167.35 for AB29 at 50 °C. These findings reveal the potential and effectiveness of the newly prepared biohybrid adsorbent for the adsorption of both dyes.

New magnetic Schiff's base-chitosan-glyoxal/fly ash/Fe3O4 biocomposite for the removal of anionic azo dye: An optimized process.

In this study, a new magnetic Schiff's base-chitosan-glyoxal/fly ash/Fe3O4 biocomposite (Chi-Gly/FA/Fe3O4) was successfully synthesized by direct compositing of magnetic chitosan (Chi) with fly ash (FA) powder particles, and followed by Schiff's base formation via cross-linking reaction with glyoxal (Gly). Various techniques such as BET, XRD, FTIR, and SEM-EDX were utilized to characterize of Chi-Gly/FA/Fe3O4 biocomposite. The effectiveness of Chi-Gly/FA/Fe3O4 as an adsorbent was evaluated for the removal anionic azo dye such as reactive orange 16 (RO16) from aqueous environment. The effect of adsorption process parameters namely adsorbent dose (A: 0.02-0.1 g), solution pH (B: 4-10), temperature (C: 30-50 °C), and contact time (D: 5-20 min) were optimized via Box-Behnken design (BBD) in response surface methodology (RSM). The adsorption process followed the pseudo-second order (PSO) kinetic, and Freundlich isotherm models. The maximum adsorption capacity of Chi-Gly/FA/Fe3O4 biocomposite for RO16 dye was recorded to be 112.5 mg/g at 40 °C. The RO16 dye adsorption mechanism was attributed to various interactions such as electrostatic, n-π, H-bonding, and Yoshida H-bonding. Furthermore, the Chi-Gly/FA/Fe3O4 biocomposite exhibited a high ability to separate from the aqueous solution after adsorption process by external magnetic field.

A review on recent trends in reactor systems and azeotrope separation strategies for catalytic conversion of biodiesel-derived glycerol.

The increasing demand for biodiesel (BD) as a renewable and sustainable energy source has impelled the generation of abundant and low-cost byproduct glycerol, which accounts for 10 wt% of total BD production and requires urgent utilization. The transesterification reaction, which utilizes glycerol and dimethyl carbonate (DMC) to synthesize valuable glycerol carbonate (GC) is an established reaction pathway to valorize oversupplied glycerol. Commercialization of inexpensive GC is constrained by the nature, stability, and basicity of applied catalyst, reaction conditions, types of the reactor system and separation methods of reaction products. This study presents a review and diversity of recent reports on reactor systems and DMC-methanol azeotrope separation strategies explored in GC synthesis from biodiesel-derived glycerol. Also, recent trends on heterogeneous catalysts, their performance, and the effects of reaction conditions were presented. Conducted studies revealed that the choice for reactor systems is constrained by factors such as energy consumption and operational safety and a significant mild reaction conditions could be realized using a microwave reactor. Furthermore, the reactive-extractive distillation and pervaporation processes showed high energy-efficiency and appreciable separation of DMC-methanol azeotrope. Thus, the development of stable catalyst and process intensification to fabricate an integrated reactor-separation system with high energy efficiency are fundamental and must be explored. This study portrays the recent research effort made in this direction and the limitations that require urgent attention.

Deoxygenation of pyrolysis vapour derived from durian shell using catalysts prepared from industrial wastes rich in Ca, Fe, Si and Al.

Catalysts prepared from industrial wastes rich in Fe, Ca, Si, and Al were used in catalytic upgrading of pyrolysis vapour derived from durian shell and their effect on product yield and properties were compared. With same silica-to-alumina ratio, catalyst prepared from oil palm ash (AS-OPA) with lower Fe and Ca contents gave higher liquid yield (8.32 wt%) with alcohols (28.90%), hydrocarbons (46.00%), and nitrogen-containing compounds (21.46%) while catalyst prepared from electric arc furnace slag (AS-EAF) with higher Fe and Ca contents produced lower liquid yield (50.21 wt%) with high amount of esters (25.80%) and hydrocarbons (72.82%). The presence of AS-OPA and AS-EAF catalysts enhanced deoxygenation degree of bio-oil to 81.13% and 85.49%, respectively. The catalytic performance of AS-EAF at different temperatures (400-600 °C) and AS-EAF/durian shell ratios (1:30, 2:30, 3:30) was investigated. Increasing catalytic temperature enhanced production of bio-oil, reduced oxygenates and enhanced formation of esters. The liquid yield and yield of esters decreased with increasing catalyst loading. Hydrocarbons (mainly neopentane) were the major chemical compounds found in bio-oil produced over AS-EAF. Besides that, AS-EAF showed good deoxygenation performance with highest selectivity of hydrocarbons at 500 °C and AS-EAF/durian shell ratio of 2:30. Catalytic fast pyrolysis of durian shell using waste-derived catalysts is an effective waste management strategy as the bio-oil produced can be a potential alternative source of energy or chemical feedstocks.

One-step synthesis of chitosan-polyethyleneimine with calcium chloride as effective adsorbent for Acid Red 88 removal.

Chitosan-polyethyleneimine with calcium chloride as ionic cross-linker (CsPC) was synthesized as a new kind of adsorbent using a simple, green and cost-effective technique. The adsorption properties of the adsorbent for Acid Red 88 (AR88) dye, as a model analyte, were investigated in a batch system as the function of solution pH (pH 3-12), initial AR88 concentration (50-500 mg L-1), contact time (0-24 h), and temperature (30-50 °C). Results showed that the adsorption process obeyed the pseudo-first order kinetic model and the adsorption rate was governed by both intra-particle and liquid-film mechanism. Equilibrium data were well correlated with the Freundlich isotherm model, with the calculated maximum adsorption capacity (qm) of 1000 mg g-1 at 30 °C. The findings underlined CsPC to be an effective and efficient adsorbent, which can be easily synthesized via one-step process with promising prospects for the removal of AR88 or any other similar dyes from the aqueous solutions.

Insights into the isotherm and kinetic models for the coadsorption of pharmaceuticals in the absence and presence of metal ions: A review.

Pharmaceuticals are a wide class of emerging pollutants due to their continuous and the increasing consumption of users. These pollutants are usually found in the real environment as mixtures alone or with metal ions. Thus, the migration risk increases, which complicates the removal of pharmaceuticals because of the combined and synergistic effects. The focus of treatment of pharmaceutical mixtures and their coexistence with metals is of considerable importance. For this purpose, adsorption has been efficiently applied to several studies for the treatment of such complex systems. In this article, the coadsorption behavior of pharmaceuticals in the absence and existence of metals on several adsorbents has been reviewed. The adsorption isotherms and kinetics of these two systems have been analyzed using different models and discussed. Important challenges and promising routes are suggested for the future development of the coadsorption of the studied systems. This article provides an overview on the most utilized and effective adsorbents, widely studied adsorbates, best applied isotherm and kinetic models, and competitive effect in coadsorption of pharmaceuticals, both with and without metals.

Chitosan-glyoxal film as a superior adsorbent for two structurally different reactive and acid dyes: Adsorption and mechanism study.

In this work, chitosan (Chi) was cross-linked with glyoxal (Gly) and deposited onto glass plate to be a superior adsorbent film for two structurally different reactive orange 16 (RO-16) and methyl orange (MO) dyes by using non-conventional adsorption system without filtration process. The characterizations indicate that the cross-linked chitosan-glyoxal (Chi-Gly) film has a low swelling index, high adherence strength on glass plate, amine group (NH2) content was 32.52%, and pHpzc of ∼6.0 indicating a negative surface charge occurs above pHpzc. The adsorption isotherm data of RO-16 and MO by Chi-Gly film were in agreement with Langmuir isotherm, with maximum adsorption capacities of 1554.3 mg/g and 1451.9 mg/g, respectively. The pseudo-first-order kinetic model best described the kinetic data. The adsorption process was spontaneous and exothermic in nature at Chi-Gly film thickness of 8.55 µm, and pH ~3. The mechanism of adsorption included mainly electrostatic attractions, dipole-dipole hydrogen bonding interactions, n-π stacking attractions, and Yoshida H-bonding. This study reveals that immobilized Chi-Gly film as a good candidate for adsorption of reactive and acid dyes as it does not require any filtration process and adsorbent recovery during and post-adsorption process.

Catalytic co-pyrolysis of sugarcane bagasse and waste high-density polyethylene over faujasite-type zeolite.

This study investigated the catalytic co-pyrolysis of sugarcane bagasse (SCB) and waste high-density polyethylene (HDPE) over faujasite-type zeolite derived from electric arc furnace slag (FAU-EAFS) in a fixed-bed reactor. The effects of reaction temperature, catalyst-to-feedstock ratio, and HDPE-to-SCB ratio on product fractional yields and chemical compositions were discussed. The co-pyrolysis of SCB and HDPE over FAU-EAFS increased the liquid yield and enhanced the quality of bio-oil. The maximum bio-oil (68.56 wt%) and hydrocarbon yield (74.55%) with minimum yield of oxygenated compounds (acid = 0.57% and ester = 0.67%) were achieved under the optimum experimental conditions of catalyst-to-feedstock ratio of 1:6, HDPE-to-SCB ratio of 40:60, and temperature of 500 °C. The oil produced by catalytic co-pyrolysis had higher calorific value than the oil produced by the pyrolysis of SCB alone.

Single-step pyrolysis of phosphoric acid-activated chitin for efficient adsorption of cephalexin antibiotic.

Cephalexin (CFX) antibiotic, a potent pharmaceutical water pollutant, was efficiently removed by activated carbon (AC) derived from a single-step pyrolysis of phosphoric acid-activated chitin. Experimental conditions such as temperature, CFX initial concentration, and solution pH were screened in batch adsorption. Phosphoric acid activation of chitin and subsequent pyrolysis tailored the Brunauer-Emmett-Teller surface area, total pore volume, and average pore diameter to 1199.02 m2/g, 0.641 cm3/g, and 21.37 Å, respectively. The Langmuir isotherm adequately described the equilibrium data for CFX adsorption on chitin-AC, with an R2 of 0.99 and a monolayer capacity of 245.19 mg/g at 50 °C. Chitin-AC showed higher adsorption capacity compared with other ACs derived from industrial and agricultural precursors. When activated by phosphoric acid, chitin-AC featured functional multi-sites for vast antibiotic adsorption treatment. Overall, chitin-AC could be a promising adsorbent for removal of CFX.

High-performance porous biochar from the pyrolysis of natural and renewable seaweed (Gelidiella acerosa) and its application for the adsorption of methylene blue.

A high-performance porous biochar adsorbent prepared by facile thermal pyrolysis of seaweed (Gelidiella acerosa) is reported. The textural characteristics of the prepared seaweed biochar (SWBC) and the performance in the adsorption of methylene blue (MB) dye were evaluated. The batch experiment for the adsorption of MB was conducted under different parameters, such as temperature, pH, and initial concentration of MB in the range of 25-400 mg/L. The developed SWBC exhibited a relatively high surface area, average pore size, and pore volume of 926.39 m2/g, 2.45 nm, and 0.57 cm3/g, respectively. The high surface area and pristine mineral constituents of the biochar promoted a high adsorption capacity of 512.67 mg/g of MB at 30 °C. The adsorption isotherm and kinetics data best fitted the Langmuir and pseudo-second-order equations. The results indicate that SWBC is efficient for MB adsorption and could be a potential adsorbent for wastewater treatment.

Catalytic fast pyrolysis of durian rind using silica-alumina catalyst: Effects of pyrolysis parameters.

Silica-alumina catalyst was prepared and used in the catalytic fast pyrolysis of durian rind in a drop-type two-stage reactor. The effects of catalytic temperature (400 °C-600 °C) and catalyst-to-durian rind ratio (1:30-3:30) were evaluated. Bio-oil yield was increased with increased catalytic temperature due to considerable dehydration process, but it was reduced with high catalyst loading due to the overcracking of organics into light gases. Silica-alumina catalyst possessed good selectivity and the products changed according to the temperature. The major components in bio-oil were hydrocarbons, furan derivatives, and aromatic compounds at 400 °C, 500 °C, and 600 °C, respectively. The hydrogen and carbon contents of bio-oil were reduced with high catalyst loading due to the overcracking of organics, and the deoxygenation process became unfavorable. The silica-alumina catalyst worked well in catalytic fast pyrolysis of durian rind, and the condition may be adjusted based on the desired products.

Removal of emerging pharmaceutical contaminants by adsorption in a fixed-bed column: A review.

Pharmaceutical pollutants substantially affect the environment; thus, their treatments have been the focus of many studies. In this article, the fixed-bed adsorption of pharmaceuticals on various adsorbents was reviewed. The experimental breakthrough curves of these pollutants under various flow rates, inlet concentrations, and bed heights were examined. Fixed-bed data in terms of saturation uptakes, breakthrough time, and the length of the mass transfer zone were included. The three most popular breakthrough models, namely, Adams-Bohart, Thomas, and Yoon-Nelson, were also reviewed for the correlation of breakthrough curve data along with the evaluation of model parameters. Compared with the Adams-Bohart model, the Thomas and Yoon-Nelson more effectively predicted the breakthrough data for the studied pollutants.

Pyrolysis of oil palm mesocarp fiber catalyzed with steel slag-derived zeolite for bio-oil production.

The pyrolysis of oil palm mesocarp fiber (OPMF) was catalyzed with a steel slag-derived zeolite (FAU-SL) in a slow-heating fixed-bed reactor at 450 °C, 550 °C, and 600 °C. The catalytic pyrolysis of OPMF produced a maximum yield of 47 wt% bio-oil at 550 °C, and the crude pyrolysis vapor (CPV) of this process yielded crude pyrolysis oil with broad distribution of bulky oxygenated organic compounds. The bio-oil composition produced at 550 °C contained mainly light and stable acid-rich carbonyls at a relative abundance of 48.02% peak area and phenolic compounds at 12.03% peak area. The FAU-SL high mesoporosity and strong surface acidity caused the conversion of the bulky CPV molecules into mostly light acid-rich carbonyls and aromatics through secondary reactions. The secondary reactions mechanisms facilitated by FAU-SL reduced the distribution of the organic compounds in the bio-oil to mostly acid-rich carbonyls and aromatic in contrast to other common zeolite.

Mercerized mesoporous date pit activated carbon-A novel adsorbent to sequester potentially toxic divalent heavy metals from water.

A substantive approach converting waste date pits to mercerized mesoporous date pit activated carbon (DPAC) and utilizing it in the removal of Cd(II), Cu(II), Pb(II), and Zn(II) was reported. In general, rapid heavy metals adsorption kinetics for Co range: 25-100 mg/L was observed, accomplishing 77-97% adsorption within 15 min, finally, attaining equilibrium in 360 min. Linear and non-linear isotherm studies revealed Langmuir model applicability for Cd(II) and Pb(II) adsorption, while Freundlich model was fitted to Zn(II) and Cu(II) adsorption. Maximum monolayer adsorption capacities (qm) for Cd(II), Pb(II), Cu(II), and Zn(II) obtained by non-linear isotherm model at 298 K were 212.1, 133.5, 194.4, and 111 mg/g, respectively. Kinetics modeling parameters showed the applicability of pseudo-second-order model. The activation energy (Ea) magnitude revealed physical nature of adsorption. Maximum elution of Cu(II) (81.6%), Zn(II) (70.1%), Pb(II) (96%), and Cd(II) (78.2%) were observed with 0.1 M HCl. Thermogravimetric analysis of DPAC showed a total weight loss (in two-stages) of 28.3%. Infra-red spectral analysis showed the presence of carboxyl and hydroxyl groups over DPAC surface. The peaks at 820, 825, 845 and 885 cm-1 attributed to Zn-O, Pb-O, Cd-O, and Cu-O appeared on heavy metals saturated DPAC, confirmed their binding on DPAC during the adsorption.

Mesoporous activated coconut shell-derived hydrochar prepared via hydrothermal carbonization-NaOH activation for methylene blue adsorption.

Mesoporous activated carbon was prepared using a hydrochar derived from coconut shell waste through hydrothermal carbonization and NaOH chemical activation process (COSHTC). Three sets of activated carbons were obtained with different hydrochar:NaOH impregnation ratios (1:1, 1:2, and 1:3). Among these ratios, 1:3 (COSHTC3) exhibited the optimum adsorption for methylene blue (MB). COSHTC3 adsorbed MB with an initial concentration of 25-250 mg/L at pH 3-11 and 30 °C. The adsorption isotherm of MB on COSHTC3 demonstrated that Langmuir isotherm could be better applied at a maximum monolayer adsorption capacity of 200.01 mg/g at 30 °C. The data was well fitted to the pseudo-second-order (PSO) kinetic model. These results show that the COSHTC3 prepared from low-cost agricultural waste (coconut shell) with average pore diameter 28.6 Å and surface area 876.14 m2/g acts as a better adsorbent for removal of cationic dyes and could pave the way for more low-cost adsorbents for dye removal.