Pub Date : 2025-12-02DOI: 10.1016/j.ceja.2025.100984
Hasan Can Gulbalkan, Seda Keskin
We integrated molecular simulations and machine learning (ML) to comprehensively explore the gas adsorption and separation performances of both synthesized and hypothetical metal-organic frameworks (MOFs) available in five different MOF databases. Following the generation of CO2, O2, and N2 adsorption data for synthesized MOFs at varying pressures through grand canonical Monte Carlo (GCMC) simulations, we developed ML models that can swiftly and accurately predict the gas adsorption properties of any MOF based on its structural, chemical, and energetic characteristics. These ML models were then transferred to four distinct hypothetical MOF databases consisting of nearly 130,000 structures to assess their CO2, O2, and N2 adsorption properties in addition to CO2/N2 and O2/N2 separation performances as a very efficient alternative to computationally time and resource demanding molecular simulations. We identified the top-performing materials from each database to uncover their structural, chemical, and topological properties leading to high selectivities and concluded that synthesized MOFs with narrow pores, lanthanide metals, and linkers featuring oxalate, pyridine dicarboxylate, and fumarate offer the highest CO2/N2 selectivities. Our work presents the most extensive dataset produced for CO2, O2, and N2 gas adsorption in MOFs, composed of ∼3.9 million data points for materials’ structural, chemical, and energetic features, gas adsorption properties, and selectivities computed at different pressures to accelerate the materials design and discovery for CO2, O2, and N2 adsorption and separation.
{"title":"Leveraging molecular simulations and machine learning to assess CO2, O2, and N2 adsorption and separation performances of diverse MOF databases","authors":"Hasan Can Gulbalkan, Seda Keskin","doi":"10.1016/j.ceja.2025.100984","DOIUrl":"10.1016/j.ceja.2025.100984","url":null,"abstract":"<div><div>We integrated molecular simulations and machine learning (ML) to comprehensively explore the gas adsorption and separation performances of both synthesized and hypothetical metal-organic frameworks (MOFs) available in five different MOF databases. Following the generation of CO<sub>2</sub>, O<sub>2</sub>, and N<sub>2</sub> adsorption data for synthesized MOFs at varying pressures through grand canonical Monte Carlo (GCMC) simulations, we developed ML models that can swiftly and accurately predict the gas adsorption properties of any MOF based on its structural, chemical, and energetic characteristics. These ML models were then transferred to four distinct hypothetical MOF databases consisting of nearly 130,000 structures to assess their CO<sub>2</sub>, O<sub>2</sub>, and N<sub>2</sub> adsorption properties in addition to CO<sub>2</sub>/N<sub>2</sub> and O<sub>2</sub>/N<sub>2</sub> separation performances as a very efficient alternative to computationally time and resource demanding molecular simulations. We identified the top-performing materials from each database to uncover their structural, chemical, and topological properties leading to high selectivities and concluded that synthesized MOFs with narrow pores, lanthanide metals, and linkers featuring oxalate, pyridine dicarboxylate, and fumarate offer the highest CO<sub>2</sub>/N<sub>2</sub> selectivities. Our work presents the most extensive dataset produced for CO<sub>2</sub>, O<sub>2</sub>, and N<sub>2</sub> gas adsorption in MOFs, composed of ∼3.9 million data points for materials’ structural, chemical, and energetic features, gas adsorption properties, and selectivities computed at different pressures to accelerate the materials design and discovery for CO<sub>2</sub>, O<sub>2</sub>, and N<sub>2</sub> adsorption and separation.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100984"},"PeriodicalIF":7.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747813","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 : 2025-12-02DOI: 10.1016/j.ceja.2025.100986
Cyrille Ghislain Fotsop, Alexandra Lieb, Franziska Scheffler
In view of the increasing demand for clean water, the aim of this work was to elucidate, by molecular Monte Carlo (MC) simulations and experimental investigations, the capture of Sr2+, In3+, Ni2+ and Co2+ in single and mixed system ions using low cost-effective zeolites based on natural kaolin. Recycled zeolites were characterized by NMR-MAS, FT-IR, XRD, SEM, EDX-mapping and TGA/DSC analysis. XRD analysis after adsorption showed that the peak intensity decreased due to the presence of adsorbed ions on the zeolite surface. NMR-MAS revealed the chemical shift of 29Si and 27Al after adsorption due to the presence of Co and Ni in the samples, which tend to affect the chemical environment of the orbital spin. The maximum capacities (Qm,exp) obtained were ∼780, ∼600, ∼1000 and ∼1300 mg/g for Sr2+, In3+, Ni2+ and Co2+, respectively. The Langmuir isotherm provided the most accurate non-linear fit to the experimental data, with an R² > 0.993, indicating that the metal ions undergo homogeneous monolayer adsorption on the adsorbent surface. The Freundlich isotherm showed the presence of multilayer adsorption and heterogeneous adsorption energy. The removal of ions was favored by ion exchange and chemical reaction on monolayers with energetic heterogeneity at the zeolite surface. Pseudo-first order non-linear kinetic models were favorable with (R2 ≥ 0.99) indicating the presence of chemisorption. MC modelling showed that ion capture was favorable in neutral media, with individual adsorption energies (dEads/dNi) of -0.03, -0.05, -5.8 and -13.8 kcal/mol for Co, Ni, Sr and In, respectively, in a mixed ion system at 298 K. The affinity of zeolite to adsorbed Co(II) on Ni(II), Al(III), Bi(III), Ca(II), In(III), Sr(II), K(I), Cd(II), Cr(III) and Pb(II) was observed by the highest values of the distribution coefficient (Kd) and low separation factor (α). The selectivity order was Co > Ni > In > Ca > Sr > Cd > Mn > Pb > K > Al > Cr > Bi. Surface and river water influenced the adsorption capacity compared to distilled and tap water. Zeolite exhibited high stability during the removal of Sr, In, Ni and Co in both single and mixed ions systems. Removal rates were found to be in the range of ∼84 % to ∼94 % and ∼55 % to ∼80 %, respectively, after the fifth cycle.
鉴于对清洁水的需求日益增加，本研究的目的是通过分子蒙特卡罗（MC）模拟和实验研究，阐明利用基于天然高岭土的低成本沸石在单一和混合体系离子中捕获Sr2+， In3+， Ni2+和Co2+。采用NMR-MAS、FT-IR、XRD、SEM、edx作图和TGA/DSC分析对回收沸石进行了表征。吸附后的XRD分析表明，由于吸附离子在沸石表面的存在，峰强度降低。核磁共振能谱分析显示，由于样品中Co和Ni的存在，29Si和27Al在吸附后发生了化学位移，这往往会影响轨道自旋的化学环境。获得的Sr2+、In3+、Ni2+和Co2+的最大容量（Qm,exp）分别为~ 780、~ 600、~ 1000和~ 1300 mg/g。Langmuir等温线对实验数据的非线性拟合最准确，R²> 0.993，表明金属离子在吸附剂表面进行了均匀的单层吸附。Freundlich等温线分析表明，吸附过程中存在多层吸附和非均相吸附。在沸石表面具有能量非均质性的单层上，离子交换和化学反应有利于离子的去除。拟一阶非线性动力学模型（R2≥0.99）表明存在化学吸附。MC模型表明，在中性介质中离子捕获是有利的，在298 K的混合离子体系中，Co、Ni、Sr和in的吸附能分别为-0.03、-0.05、-5.8和-13.8 kcal/mol。沸石对Ni（II）、Al（III）、Bi（III）、Ca（II）、In（III）、Sr（II）、K(I)、Cd（II）、Cr（III）和Pb（II）吸附Co（II）的亲和作用表现为分布系数（Kd）的最大值和分离因子（α）的低值。选择性顺序为Co >； Ni > In > Ca > Sr > Cd > Mn > Pb > K > Al > Cr > Bi。与蒸馏水和自来水相比，地表水和河水对吸附能力有影响。沸石在单离子和混合离子体系中对Sr、In、Ni和Co的脱除均表现出较高的稳定性。第五次循环后，去除率分别在~ 84% ~ ~ 94%和~ 55% ~ ~ 80%之间。
{"title":"Highly efficient removal and separation of Sr2+, Co2+, In3+ and Ni2+ in single and mixed ion systems on low-cost Zeolite, and its stability analysis: DFT and experimental investigations","authors":"Cyrille Ghislain Fotsop, Alexandra Lieb, Franziska Scheffler","doi":"10.1016/j.ceja.2025.100986","DOIUrl":"10.1016/j.ceja.2025.100986","url":null,"abstract":"<div><div>In view of the increasing demand for clean water, the aim of this work was to elucidate, by molecular Monte Carlo (MC) simulations and experimental investigations, the capture of Sr<sup>2+</sup>, In<sup>3+</sup>, Ni<sup>2+</sup> and Co<sup>2+</sup> in single and mixed system ions using low cost-effective zeolites based on natural kaolin. Recycled zeolites were characterized by NMR-MAS, FT-IR, XRD, SEM, EDX-mapping and TGA/DSC analysis. XRD analysis after adsorption showed that the peak intensity decreased due to the presence of adsorbed ions on the zeolite surface. NMR-MAS revealed the chemical shift of <sup>29</sup>Si and <sup>27</sup>Al after adsorption due to the presence of Co and Ni in the samples, which tend to affect the chemical environment of the orbital spin. The maximum capacities (Q<sub>m</sub>,<sub>exp</sub>) obtained were ∼780, ∼600, ∼1000 and ∼1300 mg/g for Sr<sup>2+</sup>, In<sup>3+</sup>, Ni<sup>2+</sup> and Co<sup>2+</sup>, respectively. The Langmuir isotherm provided the most accurate non-linear fit to the experimental data, with an R² > 0.993, indicating that the metal ions undergo homogeneous monolayer adsorption on the adsorbent surface. The Freundlich isotherm showed the presence of multilayer adsorption and heterogeneous adsorption energy. The removal of ions was favored by ion exchange and chemical reaction on monolayers with energetic heterogeneity at the zeolite surface. Pseudo-first order non-linear kinetic models were favorable with (R<sup>2</sup> ≥ 0.99) indicating the presence of chemisorption. MC modelling showed that ion capture was favorable in neutral media, with individual adsorption energies (dEads/dNi) of -0.03, -0.05, -5.8 and -13.8 kcal/mol for Co, Ni, Sr and In, respectively, in a mixed ion system at 298 K. The affinity of zeolite to adsorbed Co(II) on Ni(II), Al(III), Bi(III), Ca(II), In(III), Sr(II), K(I), Cd(II), Cr(III) and Pb(II) was observed by the highest values of the distribution coefficient (K<sub>d</sub>) and low separation factor (α). The selectivity order was Co > Ni > In > Ca > Sr > Cd > Mn > Pb > <em>K</em> > Al > Cr > Bi. Surface and river water influenced the adsorption capacity compared to distilled and tap water. Zeolite exhibited high stability during the removal of Sr, In, Ni and Co in both single and mixed ions systems. Removal rates were found to be in the range of ∼84 % to ∼94 % and ∼55 % to ∼80 %, respectively, after the fifth cycle.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100986"},"PeriodicalIF":7.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691921","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 : 2025-12-02DOI: 10.1016/j.ceja.2025.100979
Maria Montrone , Umberto Berardi , Paola Fini , Paolo Bison , Stefano Rossi , Salvatore Gambino , Marco Pugliese , Jennifer Gubitosa , Pinalysa Cosma , Vito Rizzi , Antonio Cardone , Maria Annunziata M. Capozzi
Selective management of chemico-physical properties of l-polylactic acid (L-PLA) is pivotal to broaden the application range of this polymer. As a thermally and electrically insulating polymer, its application in energy field and electronic instruments requires innovative strategies capable of selectively tune thermal and electrical properties, safeguarding mechanical properties and thermal stability. Here, we propose a molecular approach to selectively enhance thermal conductivity of l-PLA, preserving electrical insulating capacity, by incorporating a benzoindolenine-based croconaine (CR-BI) as functional photothermal additive. l-PLA@CR-BI composite solid layers were prepared via solution casting, by combining different amounts of CR-BI and comprehensively characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), UV–vis and FTIR spectroscopy, electrical, photothermal and thermophysical measurements. l-PLA@CR-BI composites displayed homogeneous coloration and a uniform CR-BI molecular dispersion inner l-PLA, with a molecular-level thermal network resulting in a strong impact on its thermal properties. Remarkably, the inclusion of only 1wt% CR-BI led to an over threefold increase in thermal diffusivity and conductivity compared to neat l-PLA. TGA evidenced a CR-BI-induced enhancement of polymer chain mobility and the formation of new crystalline domains, improving heat transfer and suggesting thermal energy storage applications. Importantly, the electrical insulating nature of l-PLA remained unchanged across all compositions. To the best of our knowledge, this work provides the first demonstration of croconaines as molecular modulators of l-PLA’s chemico-physical properties, enabling selective and efficient enhancement of thermal transport while maintaining electrical insulation- an advance with significant implications for sustainable polymer-based electronic and energy materials.
{"title":"A new L-PLA@Croconaine-based all organic composite: selective management of thermophysical properties of L-PLA by a photothermal croconaine-based molecular additive","authors":"Maria Montrone , Umberto Berardi , Paola Fini , Paolo Bison , Stefano Rossi , Salvatore Gambino , Marco Pugliese , Jennifer Gubitosa , Pinalysa Cosma , Vito Rizzi , Antonio Cardone , Maria Annunziata M. Capozzi","doi":"10.1016/j.ceja.2025.100979","DOIUrl":"10.1016/j.ceja.2025.100979","url":null,"abstract":"<div><div>Selective management of chemico-physical properties of <span>l</span>-polylactic acid (L-PLA) is pivotal to broaden the application range of this polymer. As a thermally and electrically insulating polymer, its application in energy field and electronic instruments requires innovative strategies capable of selectively tune thermal and electrical properties, safeguarding mechanical properties and thermal stability. Here, we propose a molecular approach to selectively enhance thermal conductivity of <span>l</span>-PLA, preserving electrical insulating capacity, by incorporating a benzoindolenine-based croconaine (CR-BI) as functional photothermal additive. <span>l</span>-PLA@CR-BI composite solid layers were prepared via solution casting, by combining different amounts of CR-BI and comprehensively characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), UV–vis and FTIR spectroscopy, electrical, photothermal and thermophysical measurements. <span>l</span>-PLA@CR-BI composites displayed homogeneous coloration and a uniform CR-BI molecular dispersion inner <span>l</span>-PLA, with a molecular-level thermal network resulting in a strong impact on its thermal properties. Remarkably, the inclusion of only 1wt% CR-BI led to an over threefold increase in thermal diffusivity and conductivity compared to neat <span>l</span>-PLA. TGA evidenced a CR-BI-induced enhancement of polymer chain mobility and the formation of new crystalline domains, improving heat transfer and suggesting thermal energy storage applications. Importantly, the electrical insulating nature of <span>l</span>-PLA remained unchanged across all compositions. To the best of our knowledge, this work provides the first demonstration of croconaines as molecular modulators of <span>l</span>-PLA’s chemico-physical properties, enabling selective and efficient enhancement of thermal transport while maintaining electrical insulation- an advance with significant implications for sustainable polymer-based electronic and energy materials.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100979"},"PeriodicalIF":7.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747817","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 : 2025-12-02DOI: 10.1016/j.ceja.2025.100977
Rossella Girimonte, Rosario Meduri , Antonio Cosentino , Daniele Sofia, Francesco P. Di Maio, Alberto Di Renzo
Multi-solid fluidized beds are commonly employed in industry. Conversion of solid biomass into syngas is often operated in fluidized inert material, where severe operational issues like tar condensation and aerosol formation, corrosion, fouling, are mitigated by integrating specific tar-reducing catalysts (e.g. olivine). However, the resulting ternary bed (biomass, inert and catalyst) is prone to inefficiency owing to solids’ segregation. The present study examines the fluidization and segregation behavior of mixtures of a biomass (crushed olive pits), sand and olivine of given size, shape and density, at different compositions, by an experimental characterization of the voidage, fluidization velocity intervals, vertical concentration profiles and mixing index. Interpretation of these profiles is carried out according to the Particle Segregation Model (PSM). Originally developed for segregation in two-component fluidized beds, the PSM is conceptually extended to three-component systems. Initially, the role of composition is investigated for a biomass-rich and a sand-rich mixture. Given the contrasting sizes and densities, the former system maintains its state of mixing at low olivine fractions (maximum deviation from nominal composition: ΔxS = 0.06). In the sand-rich mixture, the size-segregating behavior leads to modest segregation of the biomass and olivine towards the bed surface (ΔxB = 0.15 max deviation) and sand at the bottom (ΔxS = 0.13 max deviation). In a third examined mixture with extended olivine fraction, a similar behavior to the sand-rich mixture is observed (ΔxS = 0.27 max deviation). Both tendencies are well captured by the PSM, whose analytical formulation allows drawing triangular plots that effectively compare experimental points and equilibrium lines.
{"title":"Mixing and segregation behavior of ternary biomass-sand-olivine fluidized bed: detailed comparison between experiments and modelling predictions","authors":"Rossella Girimonte, Rosario Meduri , Antonio Cosentino , Daniele Sofia, Francesco P. Di Maio, Alberto Di Renzo","doi":"10.1016/j.ceja.2025.100977","DOIUrl":"10.1016/j.ceja.2025.100977","url":null,"abstract":"<div><div>Multi-solid fluidized beds are commonly employed in industry. Conversion of solid biomass into syngas is often operated in fluidized inert material, where severe operational issues like tar condensation and aerosol formation, corrosion, fouling, are mitigated by integrating specific tar-reducing catalysts (e.g. olivine). However, the resulting ternary bed (biomass, inert and catalyst) is prone to inefficiency owing to solids’ segregation. The present study examines the fluidization and segregation behavior of mixtures of a biomass (crushed olive pits), sand and olivine of given size, shape and density, at different compositions, by an experimental characterization of the voidage, fluidization velocity intervals, vertical concentration profiles and mixing index. Interpretation of these profiles is carried out according to the Particle Segregation Model (PSM). Originally developed for segregation in two-component fluidized beds, the PSM is conceptually extended to three-component systems. Initially, the role of composition is investigated for a biomass-rich and a sand-rich mixture. Given the contrasting sizes and densities, the former system maintains its state of mixing at low olivine fractions (maximum deviation from nominal composition: Δx<sub>S</sub> = 0.06). In the sand-rich mixture, the size-segregating behavior leads to modest segregation of the biomass and olivine towards the bed surface (Δx<sub>B</sub> = 0.15 max deviation) and sand at the bottom (Δx<sub>S</sub> = 0.13 max deviation). In a third examined mixture with extended olivine fraction, a similar behavior to the sand-rich mixture is observed (Δx<sub>S</sub> = 0.27 max deviation). Both tendencies are well captured by the PSM, whose analytical formulation allows drawing triangular plots that effectively compare experimental points and equilibrium lines.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100977"},"PeriodicalIF":7.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691905","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}
This study explored the application of biochar produced from the forestry residues Camellia oleifera (C. oleifera) shell (COS), chestnut shell (CNS), bamboo shoot shell (BBS), and walnut shell (WNS) to elucidate the dominant mechanism by which the combined effects of different lignocellulose structures and pyrolysis temperatures regulate the adsorption of H2PO4– by biochar. The forestry waste was carbonized at different pyrolysis temperatures to obtain biochars, after which the biochar properties, H2PO4– adsorption behavior, and underlying mechanisms were investigated. The results revealed that pyrolysis temperature was a key factor in enhancing the adsorption capacity of biochar for H2PO4–, as it promotes microporosity and expands the formation of specific surface area (SBET), micropore surface Area (St-plot), and pore volume (VBJH), which in turn provides more active sites for adsorption. The adsorption experiments revealed that CNS has the best adsorption capacity for H2PO4– (Qm = 117 mg g–1) because of its unique radioactive needle-like fiber bundle structure, which forms a rich pore structure at 800 °C. Quantitative contributions analysis revealed that functional group complexation (Qcom) constituted the dominant adsorption mechanism, with contributing 48 – 64 %, as evidenced by a computed free energy of – 135.48 kcal mol⁻¹. In addtion, the adsorption of H₂PO₄⁻ by CNS biochar exhibits good reusability and anti-interference capabilities. These findings demonstrate that CNS biochar has a great potential for removing phosphate from water.
{"title":"Removal of H2PO4– in water by forestry waste biochar: Preparation, characteristics, adsorption performance, and mechanism","authors":"Anxiang Huang, Zhu Liu, Shoulu Yang, Xiang Lu, Shasha Wang, Zhongwei Wang, Nengying Wu","doi":"10.1016/j.ceja.2025.100973","DOIUrl":"10.1016/j.ceja.2025.100973","url":null,"abstract":"<div><div>This study explored the application of biochar produced from the forestry residues <em>Camellia oleifera (C. oleifera)</em> shell (COS), chestnut shell (CNS), bamboo shoot shell (BBS), and walnut shell (WNS) to elucidate the dominant mechanism by which the combined effects of different lignocellulose structures and pyrolysis temperatures regulate the adsorption of H<sub>2</sub>PO<sub>4</sub><sup>–</sup> by biochar. The forestry waste was carbonized at different pyrolysis temperatures to obtain biochars, after which the biochar properties, H<sub>2</sub>PO<sub>4</sub><sup>–</sup> adsorption behavior, and underlying mechanisms were investigated. The results revealed that pyrolysis temperature was a key factor in enhancing the adsorption capacity of biochar for H<sub>2</sub>PO<sub>4</sub><sup>–</sup>, as it promotes microporosity and expands the formation of specific surface area (S<sub>BET</sub>), micropore surface Area (S<sub>t-plot</sub>), and pore volume (V<sub>BJH</sub>), which in turn provides more active sites for adsorption. The adsorption experiments revealed that CNS has the best adsorption capacity for H<sub>2</sub>PO<sub>4</sub><sup>–</sup> (Q<sub>m</sub> = 117 mg g<sup>–1</sup>) because of its unique radioactive needle-like fiber bundle structure, which forms a rich pore structure at 800 °C. Quantitative contributions analysis revealed that functional group complexation (Q<sub>com</sub>) constituted the dominant adsorption mechanism, with contributing 48 – 64 %, as evidenced by a computed free energy of – 135.48 kcal mol⁻¹. In addtion, the adsorption of H₂PO₄⁻ by CNS biochar exhibits good reusability and anti-interference capabilities. These findings demonstrate that CNS biochar has a great potential for removing phosphate from water.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100973"},"PeriodicalIF":7.1,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691919","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 : 2025-11-28DOI: 10.1016/j.ceja.2025.100971
Urszula Zielenkiewicz , Marcin Szewczyk , Hubert Salamaga , Joanna Klim , Tomasz Walter
This study introduces a novel contribution to the long-term goal of limiting global climate change by energy recovery and reduction of associated emissions in industrial-scale wastewater treatment facilities.
The upgrades implemented at the Dobrzelin sugar factory WWTP have enabled it to achieve complete water and electricity self-sufficiency by fully reusing the biogas produced from sugar fabrication wastewater. Despite substantial technological process changes, no significant differences were detected in the composition of the microbial community present in the anaerobic chamber before and after modernization (9483 vs 9437 species). Concurrently, the efficiency of biogas production per kg of reduced pollutant load improved by an average of 3.4 %, with the methane content increase reaching 10.5 %. All currently known methane synthesis pathways are present, with CO₂ and acetate-related pathways being the most dominant.
The modernisation of the Dobrzelin WWTP represents a previously unreported achievement within the context of large-scale sugar waste treatment and, more broadly, for fully operational industrial wastewater treatment facilities.
{"title":"Extremely effective self-sufficient sugar factory wastewater treatment plant and its methanogenic microbial consortium","authors":"Urszula Zielenkiewicz , Marcin Szewczyk , Hubert Salamaga , Joanna Klim , Tomasz Walter","doi":"10.1016/j.ceja.2025.100971","DOIUrl":"10.1016/j.ceja.2025.100971","url":null,"abstract":"<div><div>This study introduces a novel contribution to the long-term goal of limiting global climate change by energy recovery and reduction of associated emissions in industrial-scale wastewater treatment facilities.</div><div>The upgrades implemented at the Dobrzelin sugar factory WWTP have enabled it to achieve complete water and electricity self-sufficiency by fully reusing the biogas produced from sugar fabrication wastewater. Despite substantial technological process changes, no significant differences were detected in the composition of the microbial community present in the anaerobic chamber before and after modernization (9483 vs 9437 species). Concurrently, the efficiency of biogas production per kg of reduced pollutant load improved by an average of 3.4 %, with the methane content increase reaching 10.5 %. All currently known methane synthesis pathways are present, with CO₂ and acetate-related pathways being the most dominant.</div><div>The modernisation of the Dobrzelin WWTP represents a previously unreported achievement within the context of large-scale sugar waste treatment and, more broadly, for fully operational industrial wastewater treatment facilities.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100971"},"PeriodicalIF":7.1,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691903","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 Electrochemical anodization of stainless steels enables the fabrication of nanostructured oxide layers with high corrosion resistance and tunable functionality. Compared with conventional valve metals such as aluminum or titanium, stainless steels present greater complexity due to their multicomponent composition and stable passive films. Recent progress, including dual-step anodization, optimized electrolytes, and targeted post-treatments has made it possible to form robust, self-organized nanoporous oxides with controlled morphology and thickness. This review critically evaluates these advances, highlighting how processing parameters influence oxide composition, pore ordering, and long-term corrosion performance. The discussion integrates recent mechanistic insights with practical design strategies for catalytic, energy-storage, and protective applications. Remaining challenges related to phase stability, mechanical integrity, and scalability are identified, along with future opportunities for deploying anodized stainless steels in advanced electrochemical and energy systems.
{"title":"Electrochemical anodization of stainless steels: Advances in nanostructured oxide synthesis for corrosion-resistant and functional surfaces","authors":"Surya Prakash Gajagouni , Ranjith Bose , Imad Barsoum , Sung Oh Cho , Akram AlFantazi","doi":"10.1016/j.ceja.2025.100972","DOIUrl":"10.1016/j.ceja.2025.100972","url":null,"abstract":"<div><div>The Electrochemical anodization of stainless steels enables the fabrication of nanostructured oxide layers with high corrosion resistance and tunable functionality. Compared with conventional valve metals such as aluminum or titanium, stainless steels present greater complexity due to their multicomponent composition and stable passive films. Recent progress, including dual-step anodization, optimized electrolytes, and targeted post-treatments has made it possible to form robust, self-organized nanoporous oxides with controlled morphology and thickness. This review critically evaluates these advances, highlighting how processing parameters influence oxide composition, pore ordering, and long-term corrosion performance. The discussion integrates recent mechanistic insights with practical design strategies for catalytic, energy-storage, and protective applications. Remaining challenges related to phase stability, mechanical integrity, and scalability are identified, along with future opportunities for deploying anodized stainless steels in advanced electrochemical and energy systems.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100972"},"PeriodicalIF":7.1,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691884","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 : 2025-11-24DOI: 10.1016/j.ceja.2025.100970
Khadijah H. Alharbi
The Friedel-Crafts acylation of furan with acetic anhydride to produce 2-acylfuran is of significant industrial importance to produce key intermediates. However, the current process usually uses liquid acids that are extremely polluting as catalysts, which is problematic for the environment. As industries continue to seek environmentally friendly and cost-effective alternatives, these green catalysts heterogeneous catalysts in a solventless green process offers a sustainable approach to chemical synthetic processes hold great promise for a wide range of applications. In the present study, nanocrystalline ZSM-5 and rare-earth ion-exchanged nanocrystalline ZSM-5 were used as heterogeneous catalysts in the liquid-phase acylation of furan with acetic anhydride. The synthesized catalysts were characterized using advanced techniques, including DLS, XRD, and SEM. Under optimized conditions, the catalyst demonstrated significantly superior performance compared to previous methods, achieving 94.1 % conversion with 100 % selectivity towards the desired product, 2-acylfuran.
{"title":"Sustainable friedel-crafts acylation of furan using nanocrystalline ZSM-5: A green catalytic approach","authors":"Khadijah H. Alharbi","doi":"10.1016/j.ceja.2025.100970","DOIUrl":"10.1016/j.ceja.2025.100970","url":null,"abstract":"<div><div>The Friedel-Crafts acylation of furan with acetic anhydride to produce 2-acylfuran is of significant industrial importance to produce key intermediates. However, the current process usually uses liquid acids that are extremely polluting as catalysts, which is problematic for the environment. As industries continue to seek environmentally friendly and cost-effective alternatives, these green catalysts heterogeneous catalysts in a solventless green process offers a sustainable approach to chemical synthetic processes hold great promise for a wide range of applications. In the present study, nanocrystalline ZSM-5 and rare-earth ion-exchanged nanocrystalline ZSM-5 were used as heterogeneous catalysts in the liquid-phase acylation of furan with acetic anhydride. The synthesized catalysts were characterized using advanced techniques, including DLS, XRD, and SEM. Under optimized conditions, the catalyst demonstrated significantly superior performance compared to previous methods, achieving 94.1 % conversion with 100 % selectivity towards the desired product, 2-acylfuran.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100970"},"PeriodicalIF":7.1,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623442","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 : 2025-11-22DOI: 10.1016/j.ceja.2025.100968
Ameer Farithkhan , Jae-Hyun Kim , Mehdi Shamekhi , Alireza Razazzadeh , Myung-Jin Jung , Hao Van Bui , Gilles H. Peslherbe , Jong-Seong Bae , Se-Hun Kwon
Exploration of advanced electrocatalyst design strategies and their development to propel the efficient glucose oxidation reaction (GOR) offers a feasible replacement for the stereotypical oxygen evolution reaction, unlocking a dual-benefit platform for sustainable hydrogen production and value-added biomass conversion. For the first time, this study presents the novel functionalization of carbon cloth (CC) fibers with a MgO interlayer to strategically direct the nucleation and growth of a catalytically dynamic Co(OH)2/Ce(OH)3 system, while systematically exploring the influence of microstructural modulation and electron engineering towards enhancing bifunctional GOR-assisted water splitting activity. Among all the fabricated electrodes, the Co(OH)2/Ce(OH)3−MgO@CC delivers brilliant performance toward glucose electrolysis, driven by the synergistic interplay of densely packed, well-connected, and uniformly distributed three-dimensional Co(OH)2/Ce(OH)3 microstructures, coupled with an optimized electron architecture established by bimetallic engineering tailored for proficient GOR. Impressively, the self-supporting Co(OH)2/Ce(OH)3−MgO@CC, when configured as a glucose electrolyzer, only demands a low operating potential of 1.65 V to achieve the high current density of 100 mA cm-2, representing a 210 mV reduction compared to typical alkaline water electrolysis. Overall, this research establishes a new paradigm for innovative electrocatalyst design and paves the way for advancing next-generation materials tailored for efficient glucose oxidation electrocatalysis.
探索先进的电催化剂设计策略及其开发，以推动高效葡萄糖氧化反应（GOR），为传统的析氧反应提供了可行的替代方案，为可持续制氢和增值生物质转化提供了双重利益平台。本研究首次提出了碳布（CC）纤维与MgO中间层的新型功能化，以战略性地指导催化动态Co(OH)2/Ce(OH)3体系的成核和生长，同时系统地探索了微观结构调节和电子工程对增强双功能go辅助水裂解活性的影响。在所有制备的电极中，Co(OH)2/Ce(OH)3−MgO@CC在葡萄糖电解方面表现出色，这是由密集排列，连接良好，均匀分布的三维Co(OH)2/Ce(OH)3微结构的协同相互作用驱动的，再加上双金属工程为精通GOR而定制的优化电子结构。令人印象深刻的是，自持型Co(OH)2/Ce(OH)3−MgO@CC当配置为葡萄糖电解槽时，只需要1.65 V的低工作电位就可以实现100 mA cm-2的高电流密度，与典型的碱性电解相比，降低了210 mV。总的来说，这项研究为创新的电催化剂设计建立了一个新的范例，并为推进下一代高效葡萄糖氧化电催化材料铺平了道路。
{"title":"Morphological and electronic engineering of Co(OH)2/Ce(OH)3 electrocatalyst on ALD-enabled MgO modified carbon cloth electrode for glucose oxidation-coupled water splitting","authors":"Ameer Farithkhan , Jae-Hyun Kim , Mehdi Shamekhi , Alireza Razazzadeh , Myung-Jin Jung , Hao Van Bui , Gilles H. Peslherbe , Jong-Seong Bae , Se-Hun Kwon","doi":"10.1016/j.ceja.2025.100968","DOIUrl":"10.1016/j.ceja.2025.100968","url":null,"abstract":"<div><div>Exploration of advanced electrocatalyst design strategies and their development to propel the efficient glucose oxidation reaction (GOR) offers a feasible replacement for the stereotypical oxygen evolution reaction, unlocking a dual-benefit platform for sustainable hydrogen production and value-added biomass conversion. For the first time, this study presents the novel functionalization of carbon cloth (CC) fibers with a MgO interlayer to strategically direct the nucleation and growth of a catalytically dynamic Co(OH)<sub>2</sub>/Ce(OH)<sub>3</sub> system, while systematically exploring the influence of microstructural modulation and electron engineering towards enhancing bifunctional GOR-assisted water splitting activity. Among all the fabricated electrodes, the Co(OH)<sub>2</sub>/Ce(OH)<sub>3</sub>−MgO@CC delivers brilliant performance toward glucose electrolysis, driven by the synergistic interplay of densely packed, well-connected, and uniformly distributed three-dimensional Co(OH)<sub>2</sub>/Ce(OH)<sub>3</sub> microstructures, coupled with an optimized electron architecture established by bimetallic engineering tailored for proficient GOR. Impressively, the self-supporting Co(OH)<sub>2</sub>/Ce(OH)<sub>3</sub>−MgO@CC, when configured as a glucose electrolyzer, only demands a low operating potential of 1.65 V to achieve the high current density of 100 mA cm<sup>-2</sup>, representing a 210 mV reduction compared to typical alkaline water electrolysis. Overall, this research establishes a new paradigm for innovative electrocatalyst design and paves the way for advancing next-generation materials tailored for efficient glucose oxidation electrocatalysis.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100968"},"PeriodicalIF":7.1,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623443","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 : 2025-11-21DOI: 10.1016/j.ceja.2025.100964
Manjunath S V , Chikmagalur Raju Girish , Sreenivasa Murthy A , Shiva Prasad N , Manjunath N K , Ramya H R , Sachidananda B , Shuvanjan B , Sutheerth A
Nutrient pollution caused by elevated nitrate (NO3−) and phosphate (PO43−) concentrations is a major driver of eutrophication, while growing volumes of fly ash and ground granulated blast furnace slag (GGBS) from industrial activities presents pressing solid waste challenge. This study introduces dual-functional M40 grade of Green Concrete Composite (GCC) that functions both as structural material and as adsorbent for water treatment. GCC was fabricated by alkali-activating fly ash and GGBS, producing porous, amorphous aluminosilicate framework with tailored surface chemistry, hydroxyl and silicate groups, minor crystalline phases, thermal stability, and high point of zero charge (pHpzc). Batch adsorption experiments examined effect of contact time (0–360 min), GCC dosage (0.5–10 g/L), initial concentration (1–100 mg/L), and solution pH (3–11). Maximum adsorption capacities of 14.08 mg/g for NO3− and 4.13 mg/g for PO43− were achieved under optimal conditions (pH 6.7, 3 g/L and 60 min). Adsorption followed pseudo-second-order kinetic model and Langmuir isotherm, indicating chemisorption. Mechanistic analysis revealed NO3− removal occurred via electrostatic attraction and ion exchange, whereas PO43− uptake involved electrostatic interactions, ligand exchange, and Ca2+ induced precipitation. In multi-pollutant systems, synergistic adsorption enhanced removal to 22.37 mg/g (NO3−) and 12.90 mg/g (PO43−). GCC exhibited potential for regeneration and reusability over three cycles, with desorption efficiencies gradually decreasing for both pollutants across successive cycles. These findings highlight GCC as novel, low-cost, regenerable, and environmentally sustainable alternative to conventional adsorbents, presenting an integrated approach to water purification and industrial waste valorization.
{"title":"Valorization of fly ash and GGBS derived green concrete composite for simultaneous removal of nitrate and phosphate from aqueous systems","authors":"Manjunath S V , Chikmagalur Raju Girish , Sreenivasa Murthy A , Shiva Prasad N , Manjunath N K , Ramya H R , Sachidananda B , Shuvanjan B , Sutheerth A","doi":"10.1016/j.ceja.2025.100964","DOIUrl":"10.1016/j.ceja.2025.100964","url":null,"abstract":"<div><div>Nutrient pollution caused by elevated nitrate (NO<sub>3</sub><sup>−</sup>) and phosphate (PO<sub>4</sub><sup>3−</sup>) concentrations is a major driver of eutrophication, while growing volumes of fly ash and ground granulated blast furnace slag (GGBS) from industrial activities presents pressing solid waste challenge. This study introduces dual-functional M40 grade of Green Concrete Composite (GCC) that functions both as structural material and as adsorbent for water treatment. GCC was fabricated by alkali-activating fly ash and GGBS, producing porous, amorphous aluminosilicate framework with tailored surface chemistry, hydroxyl and silicate groups, minor crystalline phases, thermal stability, and high point of zero charge (pH<sub>pzc</sub>). Batch adsorption experiments examined effect of contact time (0–360 min), GCC dosage (0.5–10 g/L), initial concentration (1–100 mg/L), and solution pH (3–11). Maximum adsorption capacities of 14.08 mg/g for NO<sub>3</sub><sup>−</sup> and 4.13 mg/g for PO<sub>4</sub><sup>3−</sup> were achieved under optimal conditions (pH 6.7, 3 g/L and 60 min). Adsorption followed pseudo-second-order kinetic model and Langmuir isotherm, indicating chemisorption. Mechanistic analysis revealed NO<sub>3</sub><sup>−</sup> removal occurred via electrostatic attraction and ion exchange, whereas PO<sub>4</sub><sup>3−</sup> uptake involved electrostatic interactions, ligand exchange, and Ca<sup>2+</sup> induced precipitation. In multi-pollutant systems, synergistic adsorption enhanced removal to 22.37 mg/g (NO<sub>3</sub><sup>−</sup>) and 12.90 mg/g (PO<sub>4</sub><sup>3−</sup>). GCC exhibited potential for regeneration and reusability over three cycles, with desorption efficiencies gradually decreasing for both pollutants across successive cycles. These findings highlight GCC as novel, low-cost, regenerable, and environmentally sustainable alternative to conventional adsorbents, presenting an integrated approach to water purification and industrial waste valorization.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"25 ","pages":"Article 100964"},"PeriodicalIF":7.1,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691906","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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