Radioactive iodine, including I129 and I131, poses significant environmental and health risks due to its high volatility, long half-life, and water solubility, making the effective capture and storage of these substances crucial for environmental remediation and nuclear waste management. In this context, adsorption-based capture of radioiodine by porous solids has gained considerable attention. Here, we present three chemically robust pyrrole-based porous organic polymers, IISERP-POF15, IISERP-POF16, and IISERP-POF17, for efficient gaseous and solution-phase (aqueous and non-aqueous) iodine sequestration. IISERP-POF17 exhibits a high iodine uptake of 3.07 g/g in the gas phase at 70 °C, as well as effective performance in a non-aqueous medium (hexane), with an uptake of 0.47 g/g at room temperature. In aqueous solution, IISERP-POF15 shows the highest iodine uptake, reaching 2.20 g/g at room temperature. These polymers hold high chemical stability and can be readily recycled with intact iodine capacity. X-ray photoelectron spectroscopy (XPS) analysis evidenced the occurrence of I2 and polyiodides (I3–/I5–) in the post iodine-adsorbed polymers. Infrared spectroscopic investigation of the polymers upon iodine adsorption indicated a strong interaction of I2 with -OH and pyrrolic -NH of the framework. The observed I2-framework interactions were further backed by molecular simulation using Density Functional Theory (DFT) calculations.
{"title":"Hydroxyl and pyrrole functionalized polymeric frameworks for efficient aqueous and gaseous iodine sequestration","authors":"Moulidharan Ramamoorthy , Koushiki Bhattacharjee , Himan Dev Singh , Pravesh Singh Bisht , Debanjan Chakraborty , Shyamapada Nandi","doi":"10.1016/j.ceja.2025.101023","DOIUrl":"10.1016/j.ceja.2025.101023","url":null,"abstract":"<div><div>Radioactive iodine, including I<sup>129</sup> and I<sup>131</sup>, poses significant environmental and health risks due to its high volatility, long half-life, and water solubility, making the effective capture and storage of these substances crucial for environmental remediation and nuclear waste management. In this context, adsorption-based capture of radioiodine by porous solids has gained considerable attention. Here, we present three chemically robust pyrrole-based porous organic polymers, IISERP-POF15, IISERP-POF16, and IISERP-POF17, for efficient gaseous and solution-phase (aqueous and non-aqueous) iodine sequestration. IISERP-POF17 exhibits a high iodine uptake of 3.07 <em>g</em>/g in the gas phase at 70 °C, as well as effective performance in a non-aqueous medium (hexane), with an uptake of 0.47 <em>g</em>/g at room temperature. In aqueous solution, IISERP-POF15 shows the highest iodine uptake, reaching 2.20 <em>g</em>/g at room temperature. These polymers hold high chemical stability and can be readily recycled with intact iodine capacity. X-ray photoelectron spectroscopy (XPS) analysis evidenced the occurrence of I<sub>2</sub> and polyiodides (I<sub>3</sub><sup>–</sup>/I<sub>5</sub><sup>–</sup>) in the post iodine-adsorbed polymers. Infrared spectroscopic investigation of the polymers upon iodine adsorption indicated a strong interaction of I<sub>2</sub> with -OH and pyrrolic -NH of the framework. The observed I<sub>2</sub>-framework interactions were further backed by molecular simulation using Density Functional Theory (DFT) calculations.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101023"},"PeriodicalIF":7.1,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-30DOI: 10.1016/j.ceja.2025.101024
Nulee Ji, Jin Ho Lee, Jae Hyun Kim, Jae Hoon Cho, Chan Hoon Park, Sangmin Park
The modern bioindustry is increasingly focused on replacing fossil fuel–based chemical production with greener processes, with poly-4-hydroxybutyrate (P4HB) emerging as a promising alternative to conventional petrochemical plastics. Advanced kinetic models help to efficiently design, optimize, and scale-up novel bioprocesses, such as aerobic P4HB production. Notably, dissolved oxygen depletion is a frequent occurrence during P4HB production by Escherichia coli owing to the extremely high oxygen utilization rate, which limits microbial activity and causes unexpected metabolic shifts, depending on the specific operating conditions. This study proposes an explainable model for aerobic bioprocesses that integrates material balances, transport phenomena, and microbial physiology. The model considers microbial kinetics and cellular metabolism based on oxygen transfer rate (OTR)-related terms. Employing OTR-driven substrate consumption kinetics and dynamic yield coefficient variations, the model can precisely track substrate depletion, biomass growth, P4HB yield, and time-course oxygen uptake across a range of aeration conditions. Simulation with independent datasets confirmed precise prediction of the aforementioned indicators at reactor scales of up to 3 kL. Furthermore, the versatility of the model is demonstrated through estimation of the volumetric mass transfer coefficient (kLa) under actual biotic conditions without gas analysis data. The framework facilitates robust bioprocess design and optimization, scalable kLa estimation, and provides the basis for a soft sensor implementation.
{"title":"Gas transfer–driven kinetic model for aerobic poly-4-hydroxybutyrate production under dissolved oxygen–limited conditions","authors":"Nulee Ji, Jin Ho Lee, Jae Hyun Kim, Jae Hoon Cho, Chan Hoon Park, Sangmin Park","doi":"10.1016/j.ceja.2025.101024","DOIUrl":"10.1016/j.ceja.2025.101024","url":null,"abstract":"<div><div>The modern bioindustry is increasingly focused on replacing fossil fuel–based chemical production with greener processes, with poly-4-hydroxybutyrate (P4HB) emerging as a promising alternative to conventional petrochemical plastics. Advanced kinetic models help to efficiently design, optimize, and scale-up novel bioprocesses, such as aerobic P4HB production. Notably, dissolved oxygen depletion is a frequent occurrence during P4HB production by <em>Escherichia coli</em> owing to the extremely high oxygen utilization rate, which limits microbial activity and causes unexpected metabolic shifts, depending on the specific operating conditions. This study proposes an explainable model for aerobic bioprocesses that integrates material balances, transport phenomena, and microbial physiology. The model considers microbial kinetics and cellular metabolism based on oxygen transfer rate (OTR)-related terms. Employing OTR-driven substrate consumption kinetics and dynamic yield coefficient variations, the model can precisely track substrate depletion, biomass growth, P4HB yield, and time-course oxygen uptake across a range of aeration conditions. Simulation with independent datasets confirmed precise prediction of the aforementioned indicators at reactor scales of up to 3 kL. Furthermore, the versatility of the model is demonstrated through estimation of the volumetric mass transfer coefficient (<em>k</em><sub>L</sub><em>a</em>) under actual biotic conditions without gas analysis data. The framework facilitates robust bioprocess design and optimization, scalable <em>k</em><sub>L</sub><em>a</em> estimation, and provides the basis for a soft sensor implementation.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101024"},"PeriodicalIF":7.1,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-30DOI: 10.1016/j.ceja.2025.101021
Mohd Zahid Ansari , Ebtihal Youssef , Ahmed Abdala , Samer Adham , Ahmed Abdel-Wahab
A Pt-decorated bimetallic nickel-cobalt phosphide (NiCoPz) catalyst was prepared on an optimized Fe-MIL-88 framework supported on nickel foam (NF). Fe-MIL-88 was synthesized via a solvothermal method using polyvinylpyrrolidone (PVP) and subsequently annealed at 250–400 °C. A bimetallic NiCo structure was hydrothermally grown on this framework, followed by Pt deposition using table-top magnetron sputtering (TMS) and a final phosphorization to prepare Pt@NiCoPz/MIL-400. Scanning Electron Microscopy (SEM) revealed interconnected nanosheets anchored to the MIL-derived framework. X-ray Diffraction (XRD) confirmed retention of the MIL-derived structure with NiCoP phases. Transmission Electron Microscopy (TEM) and Scanning (STEM) coupled with Energy-Dispersive X-ray Spectroscopy (EDS) mapping revealed distinct lattice fringes and a homogeneous distribution of Ni, Co, P, and Pt. X-ray Photoelectron Spectroscopy (XPS) confirmed metal-phosphorus bonding, retained Fe-centers, and the persence of Pt, while Brunauer-Emmett-Teller (BET) showed a hierarchical mesoporous structure with an increased surface area. The Pt@NiCoPz/MIL-400 catalyst required an overpotential of ∼111 mV at 10 mA cm-2 and ∼181 mV at 100 mA cm-2 in 0.5 M H2SO4 with a Tafel slope of ∼56 mVdec-1. A 48-h chronoamperometric test showed reasonable stability, although partial detachment of the surface from the substrate was observed. This approach offers a promising route to efficient HER electrocatalysts, where improved interfacial adhesion could further enhance stability.
{"title":"Synergistically engineered Pt-decorated NiCo phosphide anchored on a Fe-MIL-88-derived MOF support for enhanced hydrogen evolution","authors":"Mohd Zahid Ansari , Ebtihal Youssef , Ahmed Abdala , Samer Adham , Ahmed Abdel-Wahab","doi":"10.1016/j.ceja.2025.101021","DOIUrl":"10.1016/j.ceja.2025.101021","url":null,"abstract":"<div><div>A Pt-decorated bimetallic nickel-cobalt phosphide (NiCoP<sub>z</sub>) catalyst was prepared on an optimized Fe-MIL-88 framework supported on nickel foam (NF). Fe-MIL-88 was synthesized via a solvothermal method using polyvinylpyrrolidone (PVP) and subsequently annealed at 250–400 °C. A bimetallic NiCo structure was hydrothermally grown on this framework, followed by Pt deposition using table-top magnetron sputtering (TMS) and a final phosphorization to prepare Pt@NiCoP<sub>z</sub>/MIL-400. Scanning Electron Microscopy (SEM) revealed interconnected nanosheets anchored to the MIL-derived framework. X-ray Diffraction (XRD) confirmed retention of the MIL-derived structure with NiCoP phases. Transmission Electron Microscopy (TEM) and Scanning (STEM) coupled with Energy-Dispersive X-ray Spectroscopy (EDS) mapping revealed distinct lattice fringes and a homogeneous distribution of Ni, Co, P, and Pt. X-ray Photoelectron Spectroscopy (XPS) confirmed metal-phosphorus bonding, retained Fe-centers, and the persence of Pt, while Brunauer-Emmett-Teller (BET) showed a hierarchical mesoporous structure with an increased surface area. The Pt@NiCoP<sub>z</sub>/MIL-400 catalyst required an overpotential of ∼111 mV at 10 mA cm<sup>-2</sup> and ∼181 mV at 100 mA cm<sup>-2</sup> in 0.5 M H<sub>2</sub>SO<sub>4</sub> with a Tafel slope of ∼56 mVdec<sup>-1</sup>. A 48-h chronoamperometric test showed reasonable stability, although partial detachment of the surface from the substrate was observed. This approach offers a promising route to efficient HER electrocatalysts, where improved interfacial adhesion could further enhance stability.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101021"},"PeriodicalIF":7.1,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.ceja.2025.101017
Thi H. Ho , Hien Duy Tong , Thuat T. Trinh
Congo Red (CR), a toxic azo dye, poses significant environmental hazards, making its removal from wastewater essential. Biomass-derived hydrochar is a promising adsorbent for this purpose, but the molecular influence of surface chemistry on dye adsorption remains unclear. Using molecular dynamics simulations, we systematically examined how oxygen-containing functional groups govern CR adsorption by comparing three representative hydrochar models with varying oxygen-to-carbon (O/C) ratios: a carbon-rich surface (O/C = 0.03), a hydroxyl-enriched surface (O/C = 0.55), and a realistic model reflecting experimentally observed functionality (O/C = 0.33). Our results demonstrate that hydroxyl functionalization significantly enhances adsorption capacity and efficiency. Specifically, the hydroxyl-enriched surface exhibits a 33% higher maximum adsorption capacity compared to the carbon-rich surface. Across all systems, adsorption efficiency exceeded 97% at low concentrations, with equilibrium capacities ranging from 39.0 to 839.1 mg/g. Key adsorption mechanisms include van der Waals forces, – stacking (favored over CR self-aggregation), and hydrogen bonding. Kinetic analysis reveals that the pseudo-second-order model best describes the adsorption dynamics, consistent with experimental literature. Adsorption isotherms align better with the Langmuir and Freundlich model. These findings suggest that tuning hydrochar’s surface chemistry can substantially improve its performance, offering clear design principles for next-generation adsorbents in water purification.
{"title":"Molecular mechanisms of Congo Red adsorption on hydrochar: The critical role of hydroxyl groups in dye removal","authors":"Thi H. Ho , Hien Duy Tong , Thuat T. Trinh","doi":"10.1016/j.ceja.2025.101017","DOIUrl":"10.1016/j.ceja.2025.101017","url":null,"abstract":"<div><div>Congo Red (CR), a toxic azo dye, poses significant environmental hazards, making its removal from wastewater essential. Biomass-derived hydrochar is a promising adsorbent for this purpose, but the molecular influence of surface chemistry on dye adsorption remains unclear. Using molecular dynamics simulations, we systematically examined how oxygen-containing functional groups govern CR adsorption by comparing three representative hydrochar models with varying oxygen-to-carbon (O/C) ratios: a carbon-rich surface (O/C = 0.03), a hydroxyl-enriched surface (O/C = 0.55), and a realistic model reflecting experimentally observed functionality (O/C = 0.33). Our results demonstrate that hydroxyl functionalization significantly enhances adsorption capacity and efficiency. Specifically, the hydroxyl-enriched surface exhibits a 33% higher maximum adsorption capacity compared to the carbon-rich surface. Across all systems, adsorption efficiency exceeded 97% at low concentrations, with equilibrium capacities <span><math><msub><mrow><mi>q</mi></mrow><mrow><mi>e</mi></mrow></msub></math></span> ranging from 39.0 to 839.1 mg/g. Key adsorption mechanisms include van der Waals forces, <span><math><mi>π</mi></math></span>–<span><math><mi>π</mi></math></span> stacking (favored over CR self-aggregation), and hydrogen bonding. Kinetic analysis reveals that the pseudo-second-order model best describes the adsorption dynamics, consistent with experimental literature. Adsorption isotherms align better with the Langmuir and Freundlich model. These findings suggest that tuning hydrochar’s surface chemistry can substantially improve its performance, offering clear design principles for next-generation adsorbents in water purification.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101017"},"PeriodicalIF":7.1,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-26DOI: 10.1016/j.ceja.2025.101008
Sabrina Summers, Yuanhui Zhang
Hydrothermal liquefaction enables recovery of carbon and energy from wet wastes, producing a biocrude that can be upgraded into renewable transportation fuels such as diesel and sustainable aviation fuel. However, HTL biocrude is typically featured by high heteroatom content, hindering its fuel properties. While previous work has investigated the effects of hydrotreating parameters including catalysts on heteroatom removal, this study sought to develop additional insights on their effect on upgraded fuel properties. Molybdenum alloy (CoMo, NiMo, Mo2C) and precious metal (Pt, Pd) catalysts were compared. Hydrotreating conditions from 350–450○C, 0.1–0.5 catalyst:oil weight ratio, 2–4 h, and 10–20 hydrogen:oxygen mol ratio were explored. The hydrotreated HTL biocrude demonstrated high oil, carbon, and energy yields (45–90% for all), along with up to 93 wt% total heteroatom removal (100% HDO, 89% HDS, 19% HDN). It was found that molybdenum-based catalysts had comparable performance to noble metal catalysts like platinum and palladium, achieving complete deoxygenation and producing high fractions in the gasoline, kerosene, and diesel range. Temperature, catalyst load, and retention time significantly impacted the conversion efficiency and fuel properties. Furthermore, fuel properties of the hydrotreated biocrude could be accurately predicted using a regression model with good fit (R-squared 0.85–1.00). Accordingly, hydrotreating conditions can be tuned to optimize carbon and energy recovery, target fuel ranges, and desired hydrocarbon types. This work contributes to the recovery of renewable carbon from waste biomass, enabling the advancement of circularity for transportation fuels.
{"title":"Catalytic hydrotreatment of biocrude from hydrothermal liquefaction of wet-waste: Effect of parameters and catalysts on upgraded fuel properties","authors":"Sabrina Summers, Yuanhui Zhang","doi":"10.1016/j.ceja.2025.101008","DOIUrl":"10.1016/j.ceja.2025.101008","url":null,"abstract":"<div><div>Hydrothermal liquefaction enables recovery of carbon and energy from wet wastes, producing a biocrude that can be upgraded into renewable transportation fuels such as diesel and sustainable aviation fuel. However, HTL biocrude is typically featured by high heteroatom content, hindering its fuel properties. While previous work has investigated the effects of hydrotreating parameters including catalysts on heteroatom removal, this study sought to develop additional insights on their effect on upgraded fuel properties. Molybdenum alloy (CoMo, NiMo, Mo<sub>2</sub>C) and precious metal (Pt, Pd) catalysts were compared. Hydrotreating conditions from 350–450<sup>○</sup><strong>C</strong>, 0.1–0.5 catalyst:oil weight ratio, 2–4 h, and 10–20 hydrogen:oxygen mol ratio were explored. The hydrotreated HTL biocrude demonstrated high oil, carbon, and energy yields (45–90% for all), along with up to 93 wt% total heteroatom removal (100% HDO, 89% HDS, 19% HDN). It was found that molybdenum-based catalysts had comparable performance to noble metal catalysts like platinum and palladium, achieving complete deoxygenation and producing high fractions in the gasoline, kerosene, and diesel range. Temperature, catalyst load, and retention time significantly impacted the conversion efficiency and fuel properties. Furthermore, fuel properties of the hydrotreated biocrude could be accurately predicted using a regression model with good fit (R-squared 0.85–1.00). Accordingly, hydrotreating conditions can be tuned to optimize carbon and energy recovery, target fuel ranges, and desired hydrocarbon types. This work contributes to the recovery of renewable carbon from waste biomass, enabling the advancement of circularity for transportation fuels.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101008"},"PeriodicalIF":7.1,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-26DOI: 10.1016/j.ceja.2025.101018
Longfei Shi , Yufeng Sun , Jiaoxin Xie , Hangwei Liu , Haoyu Tang , Huaijing Liu , Jingtao Liu , Yaoguo Qin , Xiaoling Tan , Yongjun Zhang
Odorant-binding proteins (OBPs) mediate insect olfactory processes by facilitating the transport of volatile compounds to odorant receptors. Searching and designing efficient ligands that bind strongly to these OBPs can help us better utilize chemical ecological strategies for the regulation and management of insects, especially in agricultural ecosystems. In the present study, a meta-analysis employing a random effects model revealed that β-ionone exhibits high binding affinity across diverse OBPs in different insect species, with most Ki values ranging from 0.63 to 25 μM. Based on the flexible structure of β-ionone, we designed and synthesized a novel derivative IA01 through Claisen-Schmidt condensation with p-anisaldehyde. It was found that IA01 demonstrated superior binding affinities toward two AlucOBPs from Apolygus lucorum, as evidenced by fluorescence competition assays and molecular docking analyses. Electroantennogram recordings indicated that IA01 elicited more stable and sustained olfactory responses compared to β-ionone and p-anisaldehyde, an effect maintained over a seven-day period. In addition, indoor behavioral experiments showed that IA01 exhibited a strong repellent effect against Chrysopa pallens, a predatory natural enemy. Field trials further validated the enhanced attractant efficacy of IA01, which consistently captured higher numbers of A. lucorum adults.We propose that the newly designed derivative based on β-ionone has potential application value in trapping mirid bug and protecting natural enemies. Utilizing such broad-spectrum ligands as lead skeletons to develop novel attractants or repellents targeting a wide range of pests will bring us a brand new pest control technology strategy.
{"title":"Rational design of β-ionone-based derivative with enhanced insect OBP affinity and field persistence for precision pest control","authors":"Longfei Shi , Yufeng Sun , Jiaoxin Xie , Hangwei Liu , Haoyu Tang , Huaijing Liu , Jingtao Liu , Yaoguo Qin , Xiaoling Tan , Yongjun Zhang","doi":"10.1016/j.ceja.2025.101018","DOIUrl":"10.1016/j.ceja.2025.101018","url":null,"abstract":"<div><div>Odorant-binding proteins (OBPs) mediate insect olfactory processes by facilitating the transport of volatile compounds to odorant receptors. Searching and designing efficient ligands that bind strongly to these OBPs can help us better utilize chemical ecological strategies for the regulation and management of insects, especially in agricultural ecosystems. In the present study, a meta-analysis employing a random effects model revealed that β-ionone exhibits high binding affinity across diverse OBPs in different insect species, with most Ki values ranging from 0.63 to 25 μM. Based on the flexible structure of β-ionone, we designed and synthesized a novel derivative IA01 through Claisen-Schmidt condensation with p-anisaldehyde. It was found that IA01 demonstrated superior binding affinities toward two AlucOBPs from <em>Apolygus lucorum</em>, as evidenced by fluorescence competition assays and molecular docking analyses. Electroantennogram recordings indicated that IA01 elicited more stable and sustained olfactory responses compared to β-ionone and p-anisaldehyde, an effect maintained over a seven-day period. In addition, indoor behavioral experiments showed that IA01 exhibited a strong repellent effect against <em>Chrysopa pallens</em>, a predatory natural enemy. Field trials further validated the enhanced attractant efficacy of IA01, which consistently captured higher numbers of <em>A. lucorum</em> adults.We propose that the newly designed derivative based on β-ionone has potential application value in trapping mirid bug and protecting natural enemies. Utilizing such broad-spectrum ligands as lead skeletons to develop novel attractants or repellents targeting a wide range of pests will bring us a brand new pest control technology strategy.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101018"},"PeriodicalIF":7.1,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-26DOI: 10.1016/j.ceja.2025.101019
Xiaoyu Fang , Shucai Zhang , Yan Xie , Meng Yao , Diannan Lu , Yakui Chen
The widespread use of methyl tert‑butyl ether (MTBE) in gasoline has led to persistent groundwater contamination. Recently, permeable reactive barriers (PRBs) have emerged as a key in situ remediation technology for treating with such contamination. Various reactive media have been employed to intercept and degrade pollutants, but their short half-lives, instability, and poor dispersion in heterogeneous geological conditions limit their effectiveness and further applications. In this study, we designed a double-column PRB system incorporating slow-release oxidants (PLA@CP-CA) and Fe-based zeolite as heterogeneous Fenton catalysts. Calcium peroxide (CaO₂) was selected as the oxidant instead of hydrogen peroxide (H₂O₂) due to its higher stability, ease of transport, and prolonged release, facilitating sustained pollutant degradation. However, the direct use of CaO₂ raises groundwater pH, so citric acid (CA) was employed as a buffer to regulate pH during CaO₂ dissolution, thereby enhancing the efficiency of the heterogeneous Fenton process. Electron paramagnetic resonance (EPR) spectroscopy and radical trapping experiments confirmed that multiple reactive species, including ·OH, O2–·, and ¹O₂, contributed synergistically to MTBE degradation. To mitigate calcium peroxide leakage, polylactic acid (PLA) was used to encapsulate the oxidant (PLA@CP-CA) under anhydrous conditions. The Box–Behnken design (BBD) in response surface methodology (RSM) optimized the PLA@CP-CA formulation, achieving an optimal H₂O₂ release capacity of 3.22 mmol/g with a mass ratio of PLA/CP/CA at 0.67:1.77:1.17. Approximately 97% of MTBE was remediated within 192 h using the double-column PRB, demonstrating the efficacy of the controlled oxidant release from PLA@CP-CA in promoting MTBE degradation. This heterogeneous Fenton system, combining PLA@CP-CA with Fe-S-1, offers a promising approach for in situ remediation in MTBE-contaminated environments.
{"title":"Calcium peroxide-enhanced fe-based zeolite for remediation of MTBE-contaminated groundwater: application in slow-release oxidant systems","authors":"Xiaoyu Fang , Shucai Zhang , Yan Xie , Meng Yao , Diannan Lu , Yakui Chen","doi":"10.1016/j.ceja.2025.101019","DOIUrl":"10.1016/j.ceja.2025.101019","url":null,"abstract":"<div><div>The widespread use of methyl tert‑butyl ether (MTBE) in gasoline has led to persistent groundwater contamination. Recently, permeable reactive barriers (PRBs) have emerged as a key in situ remediation technology for treating with such contamination. Various reactive media have been employed to intercept and degrade pollutants, but their short half-lives, instability, and poor dispersion in heterogeneous geological conditions limit their effectiveness and further applications. In this study, we designed a double-column PRB system incorporating slow-release oxidants (PLA@CP-CA) and Fe-based zeolite as heterogeneous Fenton catalysts. Calcium peroxide (CaO₂) was selected as the oxidant instead of hydrogen peroxide (H₂O₂) due to its higher stability, ease of transport, and prolonged release, facilitating sustained pollutant degradation. However, the direct use of CaO₂ raises groundwater pH, so citric acid (CA) was employed as a buffer to regulate pH during CaO₂ dissolution, thereby enhancing the efficiency of the heterogeneous Fenton process. Electron paramagnetic resonance (EPR) spectroscopy and radical trapping experiments confirmed that multiple reactive species, including ·OH, O<sub>2</sub><sup>–</sup>·, and ¹O₂, contributed synergistically to MTBE degradation. To mitigate calcium peroxide leakage, polylactic acid (PLA) was used to encapsulate the oxidant (PLA@CP-CA) under anhydrous conditions. The Box–Behnken design (BBD) in response surface methodology (RSM) optimized the PLA@CP-CA formulation, achieving an optimal H₂O₂ release capacity of 3.22 mmol/g with a mass ratio of PLA/CP/CA at 0.67:1.77:1.17. Approximately 97% of MTBE was remediated within 192 h using the double-column PRB, demonstrating the efficacy of the controlled oxidant release from PLA@CP-CA in promoting MTBE degradation. This heterogeneous Fenton system, combining PLA@CP-CA with Fe-S-1, offers a promising approach for in situ remediation in MTBE-contaminated environments.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101019"},"PeriodicalIF":7.1,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-25DOI: 10.1016/j.ceja.2025.101007
Enrica Fontananova , Francesco Galiano , Raffaella Mancuso , Daria Talarico , Gianluca Di Profio , Lorenzo Guazzelli , Christian S. Pomelli , Mario Ferraro , Raffaele Filosa , Vincenzo Formoso , Raffaele G. Agostino , Bartolo Gabriele , Alberto Figoli
Membrane technology in sustainable energy conversion and storage requires the development of tailored membranes able to conjugate high performance (ionic conductivity, perm-selectivity and durability) with acceptable costs and sustainability in their production. In this perspective, polymerizable ionic liquids (PILs) are conductive materials suitable to make high-performing and green ion-conductive membranes combining the unique properties of the ionic liquids, with the advantages of a macromolecular crosslinked polymer. This work presents a deep investigation of the structure-property relationship of phosphonium-based PILs as a functional material for anion-conducting membranes produced by casting and successive photopolymerization (almost solvent-free conditions). The PIL-based membranes prepared were dense, flexible, and completely stable after prolonged contact with water, saline and alkaline solutions. The crosslinking reaction avoided the dissolution of the membrane in water. However, mechanical test highlighted the role of water uptake on mechanical properties of the membranes. Moreover, it was also validated the possibility to blend different PILs in order to combine in synergic way the specific advantages of each component. Electrochemical impedance spectroscopy and membrane potential measurements pointed out a trade-off relationship between the ionic conductivity and perm-selectivity. Moreover, Small Angle X-ray Scattering and differential scanning calorimetry findings shed light on the role of the chemical nature of the PIL on membrane microstructure and transport properties. The main outcome of this research is the possibility to balance the low ionic resistance transport through the charged PILs, with a good stability, tailoring the chemistry of these advanced functional materials.
{"title":"Structure-property relationship of phosphonium-based polymerized ionic liquids as anion conducting membranes","authors":"Enrica Fontananova , Francesco Galiano , Raffaella Mancuso , Daria Talarico , Gianluca Di Profio , Lorenzo Guazzelli , Christian S. Pomelli , Mario Ferraro , Raffaele Filosa , Vincenzo Formoso , Raffaele G. Agostino , Bartolo Gabriele , Alberto Figoli","doi":"10.1016/j.ceja.2025.101007","DOIUrl":"10.1016/j.ceja.2025.101007","url":null,"abstract":"<div><div>Membrane technology in sustainable energy conversion and storage requires the development of tailored membranes able to conjugate high performance (ionic conductivity, perm-selectivity and durability) with acceptable costs and sustainability in their production. In this perspective, polymerizable ionic liquids (PILs) are conductive materials suitable to make high-performing and green ion-conductive membranes combining the unique properties of the ionic liquids, with the advantages of a macromolecular crosslinked polymer. This work presents a deep investigation of the structure-property relationship of phosphonium-based PILs as a functional material for anion-conducting membranes produced by casting and successive photopolymerization (almost solvent-free conditions). The PIL-based membranes prepared were dense, flexible, and completely stable after prolonged contact with water, saline and alkaline solutions. The crosslinking reaction avoided the dissolution of the membrane in water. However, mechanical test highlighted the role of water uptake on mechanical properties of the membranes. Moreover, it was also validated the possibility to blend different PILs in order to combine in synergic way the specific advantages of each component. Electrochemical impedance spectroscopy and membrane potential measurements pointed out a trade-off relationship between the ionic conductivity and perm-selectivity. Moreover, Small Angle X-ray Scattering and differential scanning calorimetry findings shed light on the role of the chemical nature of the PIL on membrane microstructure and transport properties. The main outcome of this research is the possibility to balance the low ionic resistance transport through the charged PILs, with a good stability, tailoring the chemistry of these advanced functional materials.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101007"},"PeriodicalIF":7.1,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The precise identification of trace contaminants in hydrogen is essential for safeguarding proton-exchange membrane fuel cells (PEMFCs), facilitating reliable fuel cell implementation, and advancing global energy transition objectives outlined in Sustainable Development Goal (SDG)-7, which pertains to affordable and clean energy. This review synthesizes the analytical, metrological, and operational specifications necessary for the quantification of impurities at parts-per-million (ppm) to parts-per-billion (ppb) concentrations throughout the hydrogen production, storage, transportation, and dispensing processes that are vital for achieving SDG-9 (industry, innovation, and infrastructure) and SDG-13 (climate action). Comparative evaluations of the performance of multi-detector gas chromatography (GC), laser-based spectroscopy (CRDS/FTIR), and mass-spectrometric techniques are provided, with a focus on matrix-matched calibration, interference suppression, recovery verification, and the stability of reactive species such as sulfur compounds, carbonyls, and ammonia. The review further delineates a metrologically rigorous conformity-assessment framework that incorporates integrity of sampling systems, memory mitigation strategies, preconcentration methodologies, SI-traceable calibration, uncertainty quantification, and guard-banded decision protocols to ensure robust compliance with ISO 14,687 and SAE J2719. Instead of merely reiterating numerical thresholds, the framework associates instrument capability with distinct uncertainty-aware decision protocols, thereby facilitating trustworthy quality assurance at the boundaries of specifications. Practical recommendations are offered for online and near-line monitoring systems, verification intervals, and standardized operating procedures (SOPs) to promote reproducible, auditable hydrogen quality assurance within the context of emerging clean energy infrastructures aligned with SDG objectives.
{"title":"Analytical assurance of hydrogen purity: A comprehensive framework for trace contaminant verification and conformity assessment","authors":"Yuvarajan Devarajan , Christopher Selvam D , Dimple Bahri , Divyesh Rameshbhai Vaghela , Pradeep Kumar Jangid , Sikata Samantaray , Nakul Ramanna , Kulmani Mehar","doi":"10.1016/j.ceja.2025.101015","DOIUrl":"10.1016/j.ceja.2025.101015","url":null,"abstract":"<div><div>The precise identification of trace contaminants in hydrogen is essential for safeguarding proton-exchange membrane fuel cells (PEMFCs), facilitating reliable fuel cell implementation, and advancing global energy transition objectives outlined in Sustainable Development Goal (SDG)-7, which pertains to affordable and clean energy. This review synthesizes the analytical, metrological, and operational specifications necessary for the quantification of impurities at parts-per-million (ppm) to parts-per-billion (ppb) concentrations throughout the hydrogen production, storage, transportation, and dispensing processes that are vital for achieving SDG-9 (industry, innovation, and infrastructure) and SDG-13 (climate action). Comparative evaluations of the performance of multi-detector gas chromatography (GC), laser-based spectroscopy (CRDS/FTIR), and mass-spectrometric techniques are provided, with a focus on matrix-matched calibration, interference suppression, recovery verification, and the stability of reactive species such as sulfur compounds, carbonyls, and ammonia. The review further delineates a metrologically rigorous conformity-assessment framework that incorporates integrity of sampling systems, memory mitigation strategies, preconcentration methodologies, SI-traceable calibration, uncertainty quantification, and guard-banded decision protocols to ensure robust compliance with ISO 14,687 and SAE J2719. Instead of merely reiterating numerical thresholds, the framework associates instrument capability with distinct uncertainty-aware decision protocols, thereby facilitating trustworthy quality assurance at the boundaries of specifications. Practical recommendations are offered for online and near-line monitoring systems, verification intervals, and standardized operating procedures (SOPs) to promote reproducible, auditable hydrogen quality assurance within the context of emerging clean energy infrastructures aligned with SDG objectives.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101015"},"PeriodicalIF":7.1,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-24DOI: 10.1016/j.ceja.2025.101013
M.M. Nour , Maha A. Tony , Mai K. Fouad , Hossam A. Nabwey
A sustainable and low-cost route is presented for converting potato-based starchy waste into biochar–magnetite (P-Char@Fe₃O₄) composites that function as efficient heterogeneous photo-Fenton catalysts for the degradation of the azo dye Reactive Red 195 (RR195) in textile effluents. Potato peel biochars pyrolyzed at 200–600 °C were coupled with Fe₃O₄ nanoparticles that is prepared by co-precipitation to produce P-Char200@Fe₃O₄, P-Char400@Fe₃O₄, and P-Char600@Fe₃O₄. SEM/EDS and elemental mapping confirmed the successful anchoring of Fe₃O₄ and revealed temperature-dependent dispersion and crystallinity across the carbon matrix. Catalytic screening showed a performance trend of P-Char200@Fe₃O₄ > P-Char400@Fe₃O₄ > P-Char600@Fe₃O₄, attributed to the preservation of oxygenated surface functionalities and accessible pore structures at lower/intermediate pyrolysis temperatures. Optimized operation with the robust P-Char400@Fe₃O₄ (pH 6.5, catalyst 40 mg L⁻¹, H₂O₂ 400 mg L⁻¹, UV irradiation) achieved nearly 100% RR195 removal within 20 min. The system remained tolerant to realistic conditions, showing enhanced performance with increasing temperature (32–60 °C) but declining efficiency at high dye loads or excessive H₂O₂. Kinetic analysis confirmed pseudo-first-order behavior (R² > 0.98), while Arrhenius/Eyring evaluation yielded an activation energy of 30.98 kJ mol⁻¹, positive enthalpy of activation, and negative entropy that consistent with a surface-organized, radical-mediated mechanism. The catalyst preserved about 80% efficiency after six reuse cycles, demonstrating strong magnetic recoverability and structural stability. Compared with conventional Fenton and modified systems, the agro-waste-derived P-Char@Fe₃O₄ enables rapid decolorization at near-neutral pH, reduces sludge generation, and advances circular-economy valorization of food-processing residues, highlighting its potential for scalable textile wastewater treatment.
{"title":"Green conversion of potato-based starchy waste into photocatalyst coupled nanoparticles for efficient removal of reactive red 195 dye from textile effluents","authors":"M.M. Nour , Maha A. Tony , Mai K. Fouad , Hossam A. Nabwey","doi":"10.1016/j.ceja.2025.101013","DOIUrl":"10.1016/j.ceja.2025.101013","url":null,"abstract":"<div><div>A sustainable and low-cost route is presented for converting potato-based starchy waste into biochar–magnetite (P-Char@Fe₃O₄) composites that function as efficient heterogeneous photo-Fenton catalysts for the degradation of the azo dye Reactive Red 195 (RR195) in textile effluents. Potato peel biochars pyrolyzed at 200–600 °C were coupled with Fe₃O₄ nanoparticles that is prepared by co-precipitation to produce P-Char200@Fe₃O₄, P-Char400@Fe₃O₄, and P-Char600@Fe₃O₄. SEM/EDS and elemental mapping confirmed the successful anchoring of Fe₃O₄ and revealed temperature-dependent dispersion and crystallinity across the carbon matrix. Catalytic screening showed a performance trend of P-Char200@Fe₃O₄ > <em>P</em>-Char400@Fe₃O₄ > <em>P</em>-Char600@Fe₃O₄, attributed to the preservation of oxygenated surface functionalities and accessible pore structures at lower/intermediate pyrolysis temperatures. Optimized operation with the robust P-Char400@Fe₃O₄ (pH 6.5, catalyst 40 mg L⁻¹, H₂O₂ 400 mg L⁻¹, UV irradiation) achieved nearly 100% RR195 removal within 20 min. The system remained tolerant to realistic conditions, showing enhanced performance with increasing temperature (32–60 °C) but declining efficiency at high dye loads or excessive H₂O₂. Kinetic analysis confirmed pseudo-first-order behavior (R² > 0.98), while Arrhenius/Eyring evaluation yielded an activation energy of 30.98 kJ mol⁻¹, positive enthalpy of activation, and negative entropy that consistent with a surface-organized, radical-mediated mechanism. The catalyst preserved about 80% efficiency after six reuse cycles, demonstrating strong magnetic recoverability and structural stability. Compared with conventional Fenton and modified systems, the agro-waste-derived P-Char@Fe₃O₄ enables rapid decolorization at near-neutral pH, reduces sludge generation, and advances circular-economy valorization of food-processing residues, highlighting its potential for scalable textile wastewater treatment.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 101013"},"PeriodicalIF":7.1,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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