Journal of the Taiwan Institute of Chemical Engineers最新文献

{"title":"Designing ion pair amphiphiles for biomimetic bilayer formation via the Law of Matching Water Affinity","authors":"Yi-Chen Tsai ,&nbsp;Jing-Ting Zheng ,&nbsp;Chi-cheng Chiu","doi":"10.1016/j.jtice.2025.106436","DOIUrl":"10.1016/j.jtice.2025.106436","url":null,"abstract":"<div><h3>Background:</h3><div>Ion pair amphiphiles (IPAs) are emerging as versatile biomimetic molecules capable of self-assembling into bilayer membranes, with applications in drug delivery and nanomaterial design. A critical factor influencing IPA membrane stability is the interaction strength between ionic headgroups. However, predictive frameworks to guide IPA design remain limited.</div></div><div><h3>Methods:</h3><div>In this study, we applied the Law of Matching Water Affinity (LMWA) as a thermodynamic principle to evaluate and screen IPA head group combinations. Hydration free energies of individual ions and association free energies of ion pairs were calculated using molecular dynamics simulations combined with umbrella sampling. These values were integrated into a volcano plot to identify optimal ion pairs with balanced hydration affinities. The predictions were validated through all-atom molecular dynamics simulations of IPA bilayers.</div></div><div><h3>Significant Findings:</h3><div>Our results reveal that ion pairs with matched hydration energies form more stable ionic complexes and robust bilayers. Additionally, systems with strong hydrogen bonding and symmetric headgroup geometries exhibited higher mechanical strength, as indicated by compressibility moduli and chain ordering parameters. Conversely, large hydration mismatches or anisotropic headgroups led to micelles or interdigitated structures. This study establishes a predictive LMWA-based framework for rational IPA design, facilitating efficient screening of novel vesicle systems for biomedical applications.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106436"},"PeriodicalIF":6.3,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of alkali-etched ZIF-67 metal-organic framework composite incorporated PVDF UF membranes for efficient wastewater treatment","authors":"Jayavel Murugasamy ,&nbsp;Subramaniyan Ramasundaram ,&nbsp;Nirmith Kumar Mishra ,&nbsp;A. Roniboss ,&nbsp;Arun Thirumurugan ,&nbsp;Gabriela Sandoval Hevia ,&nbsp;P.N. Poovizhi ,&nbsp;Jagadeesh Kumar Alagarasan ,&nbsp;G. Bharath ,&nbsp;Tae Hwan Oh","doi":"10.1016/j.jtice.2025.106424","DOIUrl":"10.1016/j.jtice.2025.106424","url":null,"abstract":"<div><div>Metal-organic framework (MOF)-integrated polyvinylidene fluoride (PVDF) membranes provide a viable approach for advanced water treatment as they exhibit improved hydrophilicity and permeability, as well as antifouling characteristics. PVDF-based UF (ultrafiltration) selective membranes were modified with (zeolitic imidazolate framework) ZIF and ZIFAE (alkali-etched zeolitic imidazolate framework) MOFs in this study. Incorporating ZIFAE MOF membranes demonstrated substantially lowered contact angle, enhanced porosity, and improved flux than ZIF and PVDF membranes. Among them, the pure water flux (PWF) and bovine serum albumin (BSA) rejection of ZIFAE2 were as high as 951 ± 11 L·m⁻²·h⁻¹ and 99 ± 0.5 %, respectively. Cross-sectional and top-surface SEM images confirmed that the ZIFAE membranes showed increased pore density and uniform nanoparticle distribution, which resulted in their better hydrophilicity due to the hydroxyl (-OH) and amino (-NH) functional groups. Results of secondary effluent filtration evaluations indicated less fouling resistance and a more extended operational lifespan of the ZIFAE2 membrane. Such benefits establish ZIFAE-modified membranes as sustainable, real-world, and efficient candidates for wastewater treatment and compact alternatives to traditional tertiary treatment technologies.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106424"},"PeriodicalIF":6.3,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Integration of surfactant-modified graphene oxide with metal-organic framework-9 for enhancing chromium(VI) adsorption from aqueous media","authors":"Ahmed I. Ibrahim ,&nbsp;Muhammad S. Vohra ,&nbsp;Sagheer A. Onaizi","doi":"10.1016/j.jtice.2025.106427","DOIUrl":"10.1016/j.jtice.2025.106427","url":null,"abstract":"<div><h3>Background</h3><div>Chromium(VI) is a highly toxic and carcinogenic contaminant that poses significant threats to human health and environmental safety. Its effective elimination from water requires advanced treatment strategies.</div></div><div><h3>Methods</h3><div>In this study, a novel nanocomposite CTAB@GO@ZIF-9 was synthesized by integrating cetyltrimethylammonium bromide (CTAB), graphene oxide (GO), and zeolitic imidazolate framework-9 (ZIF-9) to enhance Cr(VI) removal from aqueous solutions. Characterization confirmed the successful integration of components, along with improved structural uniformity and material dispersion. Response Surface Methodology (RSM) was employed to optimize the effects of adsorbent mass, initial Cr(VI) concentration, and adsorption temperature.</div></div><div><h3>Significant findings</h3><div>CTAB@GO@ZIF-9 demonstrated superior water stability compared to pristine ZIF-9 due to structural reinforcement by CTAB@GO. RSM optimization revealed that all investigated factors significantly influenced Cr(VI) adsorption capacity. Kinetic results followed the pseudo-second-order model (R² = 0.9643), indicating surface-controlled adsorption via active site interactions. Freundlich isotherm (R² = 0.9861) revealed heterogeneous adsorption, and Langmuir modeling showed a maximum capacity of 518.7 mg/g. Thermodynamic results confirmed a spontaneous and endothermic process. XPS and FTIR analyses indicated dominant nitrogen coordination from ZIF-9 and partial Cr(VI) reduction to Cr(III). Electrostatic attraction from CTAB also aided Cr(VI) uptake. These results validate the efficiency of CTAB@GO@ZIF-9 in Cr(VI) removal.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106427"},"PeriodicalIF":6.3,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218109","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Transforming β-cyclodextrin into a non-conventional luminophore via H2O2 oxidation and its application in detection of tetracyclines","authors":"Zhike Wang ,&nbsp;Yanan Chen ,&nbsp;Cunling Ye","doi":"10.1016/j.jtice.2025.106437","DOIUrl":"10.1016/j.jtice.2025.106437","url":null,"abstract":"<div><h3>Background</h3><div>The detection of tetracyclines (TCs) has been needed due to their irreversible damage to the environment and human health.</div></div><div><h3>Methods</h3><div>A novel non-conventional luminophore was synthesized by oxidizing β-cyclodextrin (β-CD) with H₂O₂. The oxidized β-CD (β-CD_ox) has clustering-triggered emission (CTE) property, and exhibits blue fluorescence emission in solid powder and solution. The β-CD_ox and Eu³⁺ ions were simply mixed to fabricate a ratio fluorescence probe for detection of TC, OTC and DOX. In the presence of TCs, the red fluorescence signal of Eu³⁺ was significantly amplified via the inclusion interaction of β-CD_ox and the TCs-induced antenna effect, while the blue emission of β-CD_ox was reduced, allowing the ratio probe to reliably recognize TCs.</div></div><div><h3>Findings</h3><div>Under the optimized conditions, the ratio of I₆₁₄/I₄₃₀ of the developed probe displayed wide linear ranges of 1.0–30.0 µM, 1.0–30.0 µM and 1.0–40.0 µM for TC, OTC and DOX, respectively, and the limits of detection for TC, OTC and DOX were 0.25 µM, 0.23 µM and 0.48 µM, respectively. In addition, the probe was successfully applied to detect TCs in water samples. Importantly, this study has developed non-conventional luminophores-based ratio fluorescence probe, and has expanded the potential application fields of non-conventional luminophores.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106437"},"PeriodicalIF":6.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of stilbene acrylate quaternary ammonium salt optical brighteners on the properties of ground calcium carbonate and HDPE composite materials","authors":"Jingmin Nan ,&nbsp;Maosheng Wan ,&nbsp;Li Hua ,&nbsp;Bo Wang ,&nbsp;Feiqing Rao ,&nbsp;Jialin Liang ,&nbsp;Chunquan Li","doi":"10.1016/j.jtice.2025.106438","DOIUrl":"10.1016/j.jtice.2025.106438","url":null,"abstract":"<div><h3>Background</h3><div>Improving the dispersibility and compatibility of ground calcium carbonate particles in the polymer matrix, while enhancing whiteness, is the core issue of high-value ground calcium carbonate through adding efficient surface modifiers and whitening agents.</div></div><div><h3>Methods</h3><div>Stilbene acrylate quaternary ammonium salt optical brighteners <strong>6a-d</strong> were synthesized and optimized with polyethylene glycol 300, sodium dodecyl sulfate, and sodium stearate to form integrated additives, which were used to whiten and modify ground calcium carbonate, and then was added to prepare high density polyethylene composite materials.</div></div><div><h3>Significant Findings</h3><div>The results showed that the whiteness of the processed ground calcium carbonate increased from 93.65 to 101.51, and the oil absorption value decreased from 32.4 g/100 g to 14.6 g/100 g. The filling amount of processed ground calcium carbonate reached 25 wt.% and the performance of composite materials had improved significantly. Especially, the whiteness of HDPE/<strong>6b</strong>-M-GCC increased by 24.63 %, the cold crystallization temperature increased by 1 °C, the crystallinity increased by 4.3 %, and the tensile strength increased by 13.69 %, respectively. The addition of OB <strong>6b</strong> was beneficial for improving the compatibility between modified ground calcium carbonate and high density polyethylene, thereby effectively enhancing the performance of the composite materials.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106438"},"PeriodicalIF":6.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218149","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Supramolecular shielding and hydrophilic engineering unlock ultra-stable MOF-biocatalysts for chiral compound resolution","authors":"Wenjing Zhu,&nbsp;Junyi He,&nbsp;Xuan Li,&nbsp;Qian Zhang,&nbsp;Juan Chen,&nbsp;Xin Yuan,&nbsp;Yingnan Ma,&nbsp;Bizhu Sun,&nbsp;Panliang Zhang,&nbsp;Kewen Tang","doi":"10.1016/j.jtice.2025.106435","DOIUrl":"10.1016/j.jtice.2025.106435","url":null,"abstract":"<div><h3>Background</h3><div>The kinetic resolution of enantiomers via enzymatic catalysis holds pivotal importance in chemical engineering for chiral compound production. Metal-organic frameworks (MOFs) have emerged as promising carriers for enzyme immobilization to enhance process efficiency in industrial biocatalysis. However, conventional MOFs immobilization often compromises enzymatic activity due to structural denaturation.</div></div><div><h3>Methods</h3><div>In this study, we developed a chemical engineering approach by covalently grafting methoxy polyethylene glycolamine (PEG_N) onto mesoporous UiO-66-NH₂ (m-UiO_N), constructing a reactor-like MOFs platform tailored for immobilization of Lipase PS from <em>Pseudomonas cepacia</em>. This PEGylation strategy engineered a biomimetic interface preserved enzyme conformation through supramolecular shielding, optimized mass transfer via meso-channel hydrophilicity modulation, and reinforced stability under operation conditions.</div></div><div><h3>Significant Findings</h3><div>The resultant PS@PEG_N@m-UiO_N exhibited breakthrough performance, achieving 5.2-fold activity enhancement over free lipase with 92% retention after 6 batch cycles. The hybrid catalyst demonstrated exceptional robustness across industrial-relevant conditions (50 - 70°C, organic solvents), showcasing its potential for scalable manufacturing of chiral intermediates. This interfacial engineering protocol provides a generalizable framework for designing next-generation immobilized enzyme systems in pharmaceutical and fine chemical production.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106435"},"PeriodicalIF":6.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of NiFe2O4 Phase and tribological properties on Vacuum plasma spray Cr3C2+25NiCr coating ER 2205 - 66Co26Cr5WC filler high-strength alloy plate fabricated by wire arc additive manufacturing process","authors":"M. Karthikeyan,&nbsp;R. Selvabharathi","doi":"10.1016/j.jtice.2025.106418","DOIUrl":"10.1016/j.jtice.2025.106418","url":null,"abstract":"<div><h3>Background</h3><div>In the present research effort, single-layer deposition was used to fabricate high-strength alloy plates for wire arc additive manufacturing (WAAM) procedures using 2205 (FeCr-WAAM), 66Co26Cr5WC (CoCr-WAAM), and Fe-interface metallic (Fe-IM). The study aimed to improve the mechanical characteristics and surface morphology of high-strength alloy plate samples by comparing WAAM samples with those coated using plasma spray, focusing on microstructure, hardness, porosity faults, and wear resistance.</div></div><div><h3>Methods</h3><div>Microstructural analyses were carried out using SEM and EBSD techniques. For 2205 filler wire samples, FeCr₂O₄ multiferroic spinel, γ’-austenite crystal (AC), and CrCo biomaterial phases were observed. The 66Co26Cr5WC filler showed Co-rich solid structures (CSS), martensitic ferrite transformation (MFT), and CrO₃ crystal structures under varying heat inputs. EBSD revealed that Fe-IM samples coated with plasma spray exhibited NiFe₂O₄ cubic ferromagnetic oxide, MnCr₂O₄, and MnO₄ lattice structures, while uncoated Fe-IM samples showed NiFe₂O₄, Fe₃O₄, and CoFe₂O₄ phases. Bulk texture analysis indicated that interface metallic coated surfaces (Fe-IMC₁&lt;200&gt;, Fe-IMC₂&lt;022&gt;, Fe-IMC₃&lt;111&gt;, and Fe-IMC₄&lt;311&gt;) contained more nickel and cobalt compared to outer surfaces. Inner surface layers of Fe-IM₁&lt;001&gt;, Fe-IM₂&lt;111&gt;, and Fe-IM₃&lt;110&gt; showed multiferroic CoFe structure and α-austenite crystal structure. Wear resistance and corrosion studies were performed on WAAM, WAAM-IM, and WAAM-C sample surfaces.</div></div><div><h3>Significant findings</h3><div>Compared to the 2205 filler wire samples, the Fe-IM coated samples exhibited a 14 % higher hardness value. The NiFe₂O₄ structure was found to provide protection to both inner and outer surface layers of the samples. These findings suggest that interface metallic coating and plasma spray treatment significantly enhance the mechanical and surface characteristics of WAAM-fabricated high-strength alloy components.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106418"},"PeriodicalIF":6.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-purity DEP-based multitarget separation of particles in a converging microchannel","authors":"Reza Derakhshan,&nbsp;Fatemeh Zahra Amirkhanlou,&nbsp;Abas Ramiar","doi":"10.1016/j.jtice.2025.106431","DOIUrl":"10.1016/j.jtice.2025.106431","url":null,"abstract":"<div><h3>Background</h3><div>Dielectrophoresis (DEP) is an efficient, non-invasive method for particle separation. However, most DEP devices focus on binary separation, and achieving high-purity multitarget separation remains challenging. This paper presents the design, fabrication, and characterization of a novel microfluidic device with a converging microchannel for DEP-based multiple-particle separation.</div></div><div><h3>Methods</h3><div>A custom-developed computational fluid dynamics (CFD) solver within the OpenFOAM framework was used to investigate the influence of various geometrical and operational parameters on particle separation. The design derived from numerical analysis was used to fabricate the microdevice. Experimental particle trajectories were tracked under varying conditions and compared with numerical results. The device performance was evaluated by simultaneously separating a mixture containing three different particle groups.</div></div><div><h3>Significant Findings</h3><div>A thorough comparison between experimental and numerical findings validated the high accuracy of the developed simulation model. The microdevice achieved separation purities exceeding 97 % for mixtures of 5–10–15 µm, 5–10–20 µm, and 10–15–20 µm particles at a flow rate of 3 µl/min and specific voltages (18.5 Vpp for the first two mixtures and 16 Vpp for the third). In addition to high purity, recovery rates above 95 % were also achieved for all tested mixtures at the same flow rate, confirming efficient particle collection. Furthermore, the analysis of particle trajectory deviations for sizes 5, 10, 15, and 20 µm indicates that, with further development and increasing the number of outlets to four, high-purity separation of these four particle populations can be achieved.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106431"},"PeriodicalIF":6.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218147","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"MoO3@ZIF-8 core–shell photocatalysts for the degradation of organic dye under visible-light irradiation","authors":"Xin Guo ,&nbsp;Xueqin Wang ,&nbsp;Hejin Liu ,&nbsp;Peng Qiao ,&nbsp;Meiru Zheng ,&nbsp;Yiming Li ,&nbsp;Jiaojing Zhang ,&nbsp;Mei Zhang ,&nbsp;Yanguang Chen ,&nbsp;Hua Song ,&nbsp;Fuping Feng","doi":"10.1016/j.jtice.2025.106433","DOIUrl":"10.1016/j.jtice.2025.106433","url":null,"abstract":"<div><h3>Background</h3><div>Composites of semiconductors and metal–organic frameworks (MOFs) have opened up a promising research direction in the field of photocatalysis, particularly for treating environmental pollution. Despite extensive research on MoO₃ and ZIF-8 in photocatalysis, their organic pollutant degradation efficiency remains constrained under visible light due to rapid charge carrier recombination in monocomponent systems.</div></div><div><h3>Methods</h3><div>In this study, MoO₃@MOF core–shell nanocomposites were synthesized by stirring method using MoO₃ nanorods as the semiconductor and ZIF-8 as the MOF. The physicochemical characterization results confirmed the successful growth of ZIF-8 on the MoO₃ nanorod surfaces.</div></div><div><h3>Significant findings</h3><div>The photocatalytic performance of MoO₃@ZIF-8 was analyzed by evaluating its degradation of Rhodamine B (RhB) solutions under visible light. MoO₃@ZIF-8 showed superior degradation and photocatalytic activity over pure MoO₃ or ZIF-8. The degradation rate of RhB reached 83.6 % after 120 min of visible-light irradiation. MoO₃@0.05ZIF-8 (the mass of each reagent for ZIF-8 synthesis was 0.05 g) exhibited the highest adsorption capacity among the composite materials, reaching 28.9 %. The enhanced performance originates from synergistic MoO₃-ZIF-8 interactions, demonstrating the composite's potential for photocatalytic organic pollutant degradation.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106433"},"PeriodicalIF":6.3,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218112","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal-free β-ketoenamine-based conjugated microporous polymers: rational design of robust photocatalysts for efficient organic pollutant degradation","authors":"Mohamed Gamal Mohamed ,&nbsp;Yang‐Chin Kao ,&nbsp;Shi-Quan Hong ,&nbsp;Aya Farouk Farghal ,&nbsp;Shiao-Wei Kuo","doi":"10.1016/j.jtice.2025.106434","DOIUrl":"10.1016/j.jtice.2025.106434","url":null,"abstract":"<div><h3>Background</h3><div>The rapid growth of industrialization has led to increased discharge of dye-laden wastewater, posing serious threats to aquatic ecosystems and water sustainability. Synthetic dyes like rhodamine B (RhB) and methylene blue (MB), known for their stable conjugated structures, resist biodegradation and persist in the environment. Their accumulation in water bodies harms aquatic life and can indirectly impact human health.</div></div><div><h3>Methods</h3><div>A series of metal-free β-ketoenamine-based conjugated microporous polymers (CMPs) was synthesized via Schiff-base polycondensation of an amine-terminated azobenzene monomer (AZO-2NH₂), 2,4,6-triformylphloroglucinol (TFP), and a diamino-substituted dibenzothiophene dioxide monomer (DBTD-2NH₂) under solvothermal conditions. By varying the molar feed ratio of AZO-2NH₂:TFP:DBTD-2NH₂ (2:2:1, 1.5:2:1.5, and 1:2:2), three CMP (AZO₂-TFP₂-DBTD₁, AZO_1.5-TFP₂-DBTD_1.5, AZO₁-TFP₂-DBTD₂) with tunable porosity, electronic structure, and morphology were obtained. Comprehensive spectroscopic characterization confirmed the complete formation of β-ketoenamine linkages, the successful incorporation of azo and DBTD motifs, and high chemical purity.</div></div><div><h3>Significant Findings</h3><div>Thermogravimetric analysis of AZO-TFP-DBTD CMPs revealed outstanding thermal stability (<em>T</em>_d10 up to 461 °C, char yield up to 60.8 wt%). Nitrogen sorption studies demonstrated that our AZO-TFP-DBTD CMPs exhibited hierarchical micro- and mesoporosity, with Brunauer–Emmett–Teller (BET) surface areas ranging from 110 to 125 m² g⁻¹ and dominant pore diameters of 1.7-2.0 nm. Ultraviolet photoelectron spectroscopy (UPS) and Tauc plot analyses of AZO-TFP-DBTD CMPs revealed a progressive deepening of the highest occupied molecular orbital (HOMO) level and a narrowing of the optical bandgaps (2.12-2.19 eV) as the DBTD content increased, thereby enhancing visible-light absorption. Photocatalytic evaluation using methylene blue (MB) and rhodamine B (RhB) as model dyes under visible irradiation revealed that AZO₁-TFP₂-DBTD₂ outperformed its counterparts, achieving greater than 98% degradation within 60 min and pseudo-first-order rate constants of up to 0.067 min⁻¹. Mechanistic studies identified singlet oxygen and photo-generated electrons as the primary reactive species. Recyclability tests of AZO₁-TFP₂-DBTD₂ confirmed excellent stability over three cycles with &lt;10% loss in activity. This work highlights the effectiveness of molecular engineering and monomer stoichiometry in optimizing AZO-TFP-DBTD CMP photocatalysts for water remediation.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"179 ","pages":"Article 106434"},"PeriodicalIF":6.3,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145218113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}