This study uses the electrochemical advanced oxidation process (EAOP) with persulfate to degrade 1,4-dioxane using platinum electrodes in a single- and two-compartment systems. For a two-compartment system, almost no persulfate is consumed in the anodic cell but 3.0 to 72.4 % of persulfate is decomposed at 0 to 10 V in the cathodic cell. 1,4-Dioxane removal is 90.3 % in an anode cell and 62.6 % in a cathode cell at 10 V. Persulfate is activated by a cathode but electrons released from a cathode decrease the ORP, which affects the degradation of 1,4-dioxane. Total removal is 88.0 % for the single-compartment system and 76.5 % for the two-compartment system. A two-compartment system demonstrates the roles of the anode and cathode in the degradation of the pollutant but if an EAOP is used to treat 1,4-dioxane, a single-compartment system is more practical and efficient. Hydroxyl radicals are present in the anode cell and sulfate and hydroxyl radicals are present in the cathode cell, which show that 1,4-dioxane is respectively removed via anodic oxidation and electrochemical persulfate activation. Energy consumption ranges from 1.28 to 16.11 kWh/m3. These findings confirm the mechanisms of electrochemical persulfate activation and demonstrate the potential of EAOP for wastewater treatment.
{"title":"Electrochemical activation of persulfate for the degradation of 1,4-dioxane: single- and two-compartment systems","authors":"Hung-Hsiang Chen , Shan-Yi Shen , Yi-Chun Chen , Thi-Manh Nguyen , Yu-Chu Feng , Chang-Sheng Huang , Ku-Fan Chen","doi":"10.1016/j.jiec.2025.07.056","DOIUrl":"10.1016/j.jiec.2025.07.056","url":null,"abstract":"<div><div>This study uses the electrochemical advanced oxidation process (EAOP) with persulfate to degrade 1,4-dioxane using platinum electrodes in a single- and two-compartment systems. For a two-compartment system, almost no persulfate is consumed in the anodic cell but 3.0 to 72.4 % of persulfate is decomposed at 0 to 10 V in the cathodic cell. 1,4-Dioxane removal is 90.3 % in an anode cell and 62.6 % in a cathode cell at 10 V. Persulfate is activated by a cathode but electrons released from a cathode decrease the ORP, which affects the degradation of 1,4-dioxane. Total removal is 88.0 % for the single-compartment system and 76.5 % for the two-compartment system. A two-compartment system demonstrates the roles of the anode and cathode in the degradation of the pollutant but if an EAOP is used to treat 1,4-dioxane, a single-compartment system is more practical and efficient. Hydroxyl radicals are present in the anode cell and sulfate and hydroxyl radicals are present in the cathode cell, which show that 1,4-dioxane is respectively removed via anodic oxidation and electrochemical persulfate activation. Energy consumption ranges from 1.28 to 16.11 kWh/m<sup>3</sup>. These findings confirm the mechanisms of electrochemical persulfate activation and demonstrate the potential of EAOP for wastewater treatment.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 456-467"},"PeriodicalIF":5.9,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147085","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}
Pub Date : 2025-07-28DOI: 10.1016/j.jiec.2025.07.057
Muhammad ’Adli Nor Azman , Pei Sean Goh , Yi Lin , Ahmad Fauzi Ismail , Khairulnadzmi Jamaluddin , Norafiqah Ismail , Nur Diyana Suzaimi , Adam Haziq Mohamad Fahmi
Exfoliated layered double hydroxide (LDH) nanosheets are increasingly recognized as surface-active nanomaterials capable of enhancing membrane-based wastewater treatment. Owing to their large surface area, tunable surface charge, and strong interfacial affinity, LDH-integrated membranes exhibit improved ion permeability, selectivity, and greater resistance to fouling. This review examines nanoscale exfoliation and the characteristics of LDH surfaces on membrane interactions and performance are examined in thin-film nanocomposites (TFNs), mixed matrix membranes (MMMs) and supported LDH membranes. Exfoliation techniques—chemical, mechanical, thermal and electrochemical—are compared concerning their effects on nanosheet morphology, dispersion stability, and surface charge. Particular attention is given to radiation-assisted exfoliation, which offers a scalable, environmentally benign route for producing well-dispersed LDH suspensions. Furthermore, interfacial strategies such as polymeric coatings and layer-by-layer (LbL) assembly are discussed for their role in minimizing nanosheet aggregation and improving compatibility with polymers. The review also addresses current challenges, including nanosheet stability and the seamless integration into membrane fabrication processes. Emerging pathways that connect laboratory-scale findings with industrial implementation are discussed. From a materials engineering and sustainability perspective, exfoliated LDH nanosheets are presented as promising nanomaterials for developing next-generation membranes targeted at efficient water purification and environmental protection.
{"title":"Exfoliated LDH nanosheets for membrane-based wastewater treatment: surface engineering and performance","authors":"Muhammad ’Adli Nor Azman , Pei Sean Goh , Yi Lin , Ahmad Fauzi Ismail , Khairulnadzmi Jamaluddin , Norafiqah Ismail , Nur Diyana Suzaimi , Adam Haziq Mohamad Fahmi","doi":"10.1016/j.jiec.2025.07.057","DOIUrl":"10.1016/j.jiec.2025.07.057","url":null,"abstract":"<div><div>Exfoliated layered double hydroxide (LDH) nanosheets are increasingly recognized as surface-active nanomaterials capable of enhancing membrane-based wastewater treatment. Owing to their large surface area, tunable surface charge, and strong interfacial affinity, LDH-integrated membranes exhibit improved ion permeability, selectivity, and greater resistance to fouling. This review examines nanoscale exfoliation and the characteristics of LDH surfaces on membrane interactions and performance are examined in thin-film nanocomposites (TFNs), mixed matrix membranes (MMMs) and supported LDH membranes. Exfoliation techniques—chemical, mechanical, thermal and electrochemical—are compared concerning their effects on nanosheet morphology, dispersion stability, and surface charge. Particular attention is given to radiation-assisted exfoliation, which offers a scalable, environmentally benign route for producing well-dispersed LDH suspensions. Furthermore, interfacial strategies such as polymeric coatings and layer-by-layer (LbL) assembly are discussed for their role in minimizing nanosheet aggregation and improving compatibility with polymers. The review also addresses current challenges, including nanosheet stability and the seamless integration into membrane fabrication processes. Emerging pathways that connect laboratory-scale findings with industrial implementation are discussed. From a materials engineering and sustainability perspective, exfoliated LDH nanosheets are presented as promising nanomaterials for developing next-generation membranes targeted at efficient water purification and environmental protection.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 89-109"},"PeriodicalIF":5.9,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147376","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}
Pub Date : 2025-07-28DOI: 10.1016/j.jiec.2025.07.052
Maira Aslam , Muhammad Zain Ali , Muhammad Umair Akram , Ayesha Akram , Laiba Laiba , Sonia Naz , Francis Verpoort
The potential applications of a family of porous substances called metal–organic frameworks (MOFs) in chemical sensing have sparked a great deal of attention. The creation and synthesis of MOFs using a range of techniques, such as traditional procedures, microwave synthesis, electrochemical synthesis, mechanocompaction, and sonochemical synthesis, are examined in this thorough overview. The paper addresses contemporary issues in the field of chemical sensing while highlighting the principles of the subject and exploring the definition, significance, and necessary specifications of chemical sensor devices. The discussion then turns to MOFs as cutting-edge chemical sensing materials, explaining their special qualities, advantages, and future prospects in relation to other materials. The investigation encompasses electrical, electrochemical, electromechanical, and optical sensing techniques, as well as intrinsic and extrinsic MOF-based optical fiber sensors, and uses of MOF films and devices in chemical sensing. The topic of integrating MOFs into analytical devices is covered, with a focus on optimizing the integration of optical and electrical devices. Solid-state sensing applications using MOF-based sensors are used as examples. The study also describes developments in MOF-based wearables and smartphone sensors.
{"title":"MOFs for (bio)chemical sensor devices","authors":"Maira Aslam , Muhammad Zain Ali , Muhammad Umair Akram , Ayesha Akram , Laiba Laiba , Sonia Naz , Francis Verpoort","doi":"10.1016/j.jiec.2025.07.052","DOIUrl":"10.1016/j.jiec.2025.07.052","url":null,"abstract":"<div><div>The potential applications of a family of porous substances called metal–organic frameworks (MOFs) in chemical sensing have sparked a great deal of attention. The creation and synthesis of MOFs using a range of techniques, such as traditional procedures, microwave synthesis, electrochemical synthesis, mechanocompaction, and sonochemical synthesis, are examined in this thorough overview. The paper addresses contemporary issues in the field of chemical sensing while highlighting the principles of the subject and exploring the definition, significance, and necessary specifications of chemical sensor devices. The discussion then turns to MOFs as cutting-edge chemical sensing materials, explaining their special qualities, advantages, and future prospects in relation to other materials. The investigation encompasses electrical, electrochemical, electromechanical, and optical sensing techniques, as well as intrinsic and extrinsic MOF-based optical fiber sensors, and uses of MOF films and devices in chemical sensing. The topic of integrating MOFs into analytical devices is covered, with a focus on optimizing the integration of optical and electrical devices. Solid-state sensing applications using MOF-based sensors are used as examples. The study also describes developments in MOF-based wearables and smartphone sensors.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 52-88"},"PeriodicalIF":5.9,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147375","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}
The release of toxic azo dyes from industrial activities poses significant environmental and health risks, driving the need for advanced wastewater treatment methods. This study explores two hybrid bentonites hexadecylpyridinium-modified bentonite (HDP-B), using a cationic surfactant, and trioctylmethylammonium-modified bentonite (TOMA-B), using an ionic liquid for the removal of Congo Red (CR) dye from aqueous solutions. By varying the modification ratios relative to the cation exchange capacity (0.5, 1, and 2 times), HDP-B demonstrated a high adsorption capacity (275.15 mg g−1) due to enhanced hydrophobic interactions. Adsorption kinetics and isotherm analyses revealed pseudo-second-order behavior for 1.0TOMA-B and Elovich model compliance for 1.0HDP-B. Optimization using Response Surface Methodology-Box Behnken Design (RSM-BBD) achieved 97.49 % and 91.44 % removal efficiencies for HDP-B and TOMA-B, respectively, at pH 6 within 120 min. Thermodynamic analysis confirmed spontaneous, endothermic adsorption. DFT calculations revealed HDP-B’s superior electronic coupling with Congo Red (Δμ = 0.22 eV), consistent with its higher experimental adsorption capacity. The adsorption results are encouraging, highlighting the potential of modified adsorbents as efficient and reusable materials for CR dye removal from polluted water due to their high adsorption capacities.
{"title":"Dual functionalization of bentonite with surfactant and ionic liquid for enhanced Congo red removal: RSM optimization and mechanistic insights","authors":"Brahim Guezzen , Rachida Berrezouk , Abdelkrim Guendouzi , Baghdad Medjahed , Fouad Guenfoud , Hadja Alia Tabti , Rafik Abdelkrim Boudia , Mehdi Adjdir","doi":"10.1016/j.jiec.2025.07.055","DOIUrl":"10.1016/j.jiec.2025.07.055","url":null,"abstract":"<div><div>The release of toxic azo dyes from industrial activities poses significant environmental and health risks, driving the need for advanced wastewater treatment methods. This study explores two hybrid bentonites hexadecylpyridinium-modified bentonite (HDP-B), using a cationic surfactant, and trioctylmethylammonium-modified bentonite (TOMA-B), using an ionic liquid for the removal of Congo Red (CR) dye from aqueous solutions. By varying the modification ratios relative to the cation exchange capacity (0.5, 1, and 2 times), HDP-B demonstrated a high adsorption capacity (275.15 mg g<sup>−1</sup>) due to enhanced hydrophobic interactions. Adsorption kinetics and isotherm analyses revealed pseudo-second-order behavior for 1.0TOMA-B and Elovich model compliance for 1.0HDP-B. Optimization using Response Surface Methodology-Box Behnken Design (RSM-BBD) achieved 97.49 % and 91.44 % removal efficiencies for HDP-B and TOMA-B, respectively, at pH 6 within 120 min. Thermodynamic analysis confirmed spontaneous, endothermic adsorption. DFT calculations revealed HDP-B’s superior electronic coupling with Congo Red (Δμ = 0.22 eV), consistent with its higher experimental adsorption capacity. The adsorption results are encouraging, highlighting the potential of modified adsorbents as efficient and reusable materials for CR dye removal from polluted water due to their high adsorption capacities.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 434-455"},"PeriodicalIF":5.9,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147088","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}
Pub Date : 2025-07-26DOI: 10.1016/j.jiec.2025.07.054
Mohammad Salehi Maleh , Alireza Bahrami , Mohammad Sajad Sepehri Sadeghian , Hoda Asadimanesh , Mohtada Sadrzadeh
Two-dimensional nanomaterials (2DNMs) are promising for mixed matrix membranes (MMMs) in gas separation but face challenges such as aggregation, interfacial defects, plasticization, and aging. The present review examines key obstacles and strategies to enhance 2DNM-polymer interactions, aiming for durable, high-efficiency membranes. To address such challenges, multifaceted strategies aimed at enhancing the interfacial interaction between 2DNMs and the polymer matrix are examined. Optimizing intrinsic 2DNM properties, pore size, interlayer spacing, and lateral-to-thickness ratio, can improve gas selectivity. Controlling the number of layers, enhancing solubility, and leveraging facilitated transport properties are also crucial. Surface functionalization, such as grafting ionic liquids or macromolecules, enhances compatibility while blending chain molecules fine-tunes membrane performance. Synergistic combinations of 2DNMs with other nanomaterials, including 0D, 1D, and 3D structures, significantly improve gas transport and mechanical strength. Additionally, orientation enhancement techniques, such as applying magnetic or electric fields during fabrication, align 2DNMs within the matrix to optimize gas separation pathways. The insights gained from the study of 2DNMs extend beyond CO2 separation and are applicable to other gas mixtures. Such principles play a crucial role in shaping the next generation of MMMs, with broad implications for industrial and environmental applications.
{"title":"A comprehensive review on two-dimensional nanomaterials-mixed matrix membranes for sustainable CO2 separation: from molecular engineering design to efficient modification strategies","authors":"Mohammad Salehi Maleh , Alireza Bahrami , Mohammad Sajad Sepehri Sadeghian , Hoda Asadimanesh , Mohtada Sadrzadeh","doi":"10.1016/j.jiec.2025.07.054","DOIUrl":"10.1016/j.jiec.2025.07.054","url":null,"abstract":"<div><div>Two-dimensional nanomaterials (2DNMs) are promising for mixed matrix membranes (MMMs) in gas separation but face challenges such as aggregation, interfacial defects, plasticization, and aging. The present review examines key obstacles and strategies to enhance 2DNM-polymer interactions, aiming for durable, high-efficiency membranes. To address such challenges, multifaceted strategies aimed at enhancing the interfacial interaction between 2DNMs and the polymer matrix are examined. Optimizing intrinsic 2DNM properties, pore size, interlayer spacing, and lateral-to-thickness ratio, can improve gas selectivity. Controlling the number of layers, enhancing solubility, and leveraging facilitated transport properties are also crucial. Surface functionalization, such as grafting ionic liquids or macromolecules, enhances compatibility while blending chain molecules fine-tunes membrane performance. Synergistic combinations of 2DNMs with other nanomaterials, including 0D, 1D, and 3D structures, significantly improve gas transport and mechanical strength. Additionally, orientation enhancement techniques, such as applying magnetic or electric fields during fabrication, align 2DNMs within the matrix to optimize gas separation pathways. The insights gained from the study of 2DNMs extend beyond CO<sub>2</sub> separation and are applicable to other gas mixtures. Such principles play a crucial role in shaping the next generation of MMMs, with broad implications for industrial and environmental applications.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 110-146"},"PeriodicalIF":5.9,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147378","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}
Pub Date : 2025-07-25DOI: 10.1016/j.jiec.2025.07.040
Hayder Ghanim Chfat , Mohammad Mahtab Alam , Talib H. Mawat , Rustamkhon Kuryazov , Shatha abd aljabbar Ismael , Hussein Ali Al-Bahrani , Abdullah Yahya Abdullah Alzahrani , Mohammed Muayad T.A , Elyor Berdimurodov , Jasur Tursunqulov , Qais R. Lahhob , Lala Gurbanova
The increasing costs and environmental impact of raw materials, reagents, catalysts and solvents in organic syntheses have prompted the need for more sustainable and cost-effective approaches. In this study, we present the design and synthesis of a new multifunctional chiral SHNFM–CuCl3 DES, which serves as a solvent, electrolyte, and chiral catalyst for electro-catalytic asymmetric carboxylation reactions. This electro-catalyst system was developed using inexpensive and readily available raw materials and is utilized in the presence of graphite rod electrodes. The DES system was thoroughly characterized using FT-IR, TGA, and 1HNMR, 13CNMR to confirm its structural integrity and composition. The electro-organic synthesis of (R)-1-formyl-2-oxo-3-phenylindoline-3-carboxylic acid derivatives 3(a–i) was optimized under ambient temperature conditions, with a reaction time of 1.5 h and an applied current of 10 mA, resulting in high yields ranging from 89 % to 97 %. The final products were characterized and confirmed by FT-IR spectroscopy, measurement of optical rotation, 1HNMR spectroscopy, and elemental analysis (CHN). This work demonstrates the potential of using multifunctional DES as an efficient, environmentally friendly approach to electrochemical synthesis, reducing chemical consumption, lowering costs, and minimizing environmental impact, in line with the principles of green chemistry.
{"title":"Design of an environmentally friendly new chiral SHNFM–CuCl3 DES as solvent, electrolyte, and catalyst for electro-catalytic asymmetric carboxylation","authors":"Hayder Ghanim Chfat , Mohammad Mahtab Alam , Talib H. Mawat , Rustamkhon Kuryazov , Shatha abd aljabbar Ismael , Hussein Ali Al-Bahrani , Abdullah Yahya Abdullah Alzahrani , Mohammed Muayad T.A , Elyor Berdimurodov , Jasur Tursunqulov , Qais R. Lahhob , Lala Gurbanova","doi":"10.1016/j.jiec.2025.07.040","DOIUrl":"10.1016/j.jiec.2025.07.040","url":null,"abstract":"<div><div>The increasing costs and environmental impact of raw materials, reagents, catalysts and solvents in organic syntheses have prompted the need for more sustainable and cost-effective approaches. In this study, we present the design and synthesis of a new multifunctional chiral SHNFM–CuCl<sub>3</sub> DES, which serves as a solvent, electrolyte, and chiral catalyst for electro-catalytic asymmetric carboxylation reactions. This electro-catalyst system was developed using inexpensive and readily available raw materials and is utilized in the presence of graphite rod electrodes. The DES system was thoroughly characterized using FT-IR, TGA, and 1HNMR, 13CNMR to confirm its structural integrity and composition. The electro-organic synthesis of (R)-1-formyl-2-oxo-3-phenylindoline-3-carboxylic acid derivatives <strong>3(a–i)</strong> was optimized under ambient temperature conditions, with a reaction time of 1.5 h and an applied current of 10 mA, resulting in high yields ranging from 89 % to 97 %. The final products were characterized and confirmed by FT-IR spectroscopy, measurement of optical rotation, 1HNMR spectroscopy, and elemental analysis (CHN). This work demonstrates the potential of using multifunctional DES as an efficient, environmentally friendly approach to electrochemical synthesis, reducing chemical consumption, lowering costs, and minimizing environmental impact, in line with the principles of green chemistry.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"154 ","pages":"Pages 748-761"},"PeriodicalIF":5.9,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145924552","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}
Pub Date : 2025-07-25DOI: 10.1016/j.jiec.2025.07.053
Hannington Nevin Otieno , Samuel Daniel , Liaqat Aqsa , Zhen-Yu Tian
The oxidative dehydrogenation of propane with CO2 is an attractive approach for efficient propene production while concurrently facilitating the reduction of CO2. However, a limited understanding of the nature of active sites and structure–activity relationships continues to pose challenges for the rational design of high-performance catalysts in this sustainable process. This study elucidates the interplay between Cr and Co metal oxides in CrCo binary oxide catalysts by varying the Cr/Co weight ratio. Cr4Co1 catalyst, which contains a high Cr concentration, demonstrated the highest activity, achieving 31 ± 1 % propane conversion and 66 ± 1 % propene selectivity. This is due to the high abundance of lattice oxygen, Cr3+/Cr6+, and Co3+ species. The higher OLat/OAds ratio in the Cr4Co1 catalyst facilitates hydrogen abstraction from the propane’s C–H bond, resulting in propene formation and oxygen vacancies on the surface of the catalyst. Simultaneously, the Cr3+/Cr6+ species promote C–H bond cleavage while suppressing C–C bond cleavage. In contrast, the Co3+ species enhances the dissociation of the C=O bond in CO2. The resulting O* radicals effectively replenish the oxygen vacancies, completing the redox cycle. The interplay among these species contributes to the promising catalytic performance of CO2-ODHP. These insights provide essential guidelines for the development of high-performance CrCo-based catalysts for CO2-ODHP.
{"title":"Redox synergy of Cr3+/Co3+ in Cr-Co binary oxide: lattice oxygen dynamics for CO2-mediated oxidative dehydrogenation of propane","authors":"Hannington Nevin Otieno , Samuel Daniel , Liaqat Aqsa , Zhen-Yu Tian","doi":"10.1016/j.jiec.2025.07.053","DOIUrl":"10.1016/j.jiec.2025.07.053","url":null,"abstract":"<div><div>The oxidative dehydrogenation of propane with CO<sub>2</sub> is an attractive approach for efficient propene production while concurrently facilitating the reduction of CO<sub>2</sub>. However, a limited understanding of the nature of active sites and structure–activity relationships continues to pose challenges for the rational design of high-performance catalysts in this sustainable process. This study elucidates the interplay between Cr and Co metal oxides in CrCo binary oxide catalysts by varying the Cr/Co weight ratio. Cr<sub>4</sub>Co<sub>1</sub> catalyst, which contains a high Cr concentration, demonstrated the highest activity, achieving 31 ± 1 % propane conversion and 66 ± 1 % propene selectivity. This is due to the high abundance of lattice oxygen, Cr<sup>3+</sup>/Cr<sup>6+</sup>, and Co<sup>3+</sup> species. The higher O<sub>Lat</sub>/O<sub>Ads</sub> ratio in the Cr<sub>4</sub>Co<sub>1</sub> catalyst facilitates hydrogen abstraction from the propane’s C–H bond, resulting in propene formation and oxygen vacancies on the surface of the catalyst. Simultaneously, the Cr<sup>3+</sup>/Cr<sup>6+</sup> species promote C–H bond cleavage while suppressing C–C bond cleavage. In contrast, the Co<sup>3+</sup> species enhances the dissociation of the C=O bond in CO<sub>2</sub>. The resulting O* radicals effectively replenish the oxygen vacancies, completing the redox cycle. The interplay among these species contributes to the promising catalytic performance of CO<sub>2</sub>-ODHP. These insights provide essential guidelines for the development of high-performance CrCo-based catalysts for CO<sub>2</sub>-ODHP.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 420-433"},"PeriodicalIF":5.9,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147087","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}
Pub Date : 2025-07-23DOI: 10.1016/j.jiec.2025.07.049
Fengjiao Quan , Pengfei Xu , Xiufan Liu , Wenjuan Shen , Yuhao Li , Jianfen Li , Yun He , Fangyuan Chen
Nitrate (NO3−) pollution in groundwater has emerged as a pressing environmental issue of global concern. The excessive application of chemical fertilizers is widely recognized as the primary contributor to this pollution Nitrate ions pose significant risks to human health and the ecological environment. Electrochemical reduction of NO3− to NH3 (NITRR) represents an effective approach for nitrogen recovery and recycling. Among many electrode materials, copper-based catalysts were considered promising due to their low cost and strong NO3− conversion capability. However, excessively strong adsorption can lead to catalyst deactivation, thereby diminishing catalytic activity. In this study, we developed an electrode material (Cu@NiO/NF) with low-valent copper (Cuδ+) through the combination of Cu and NiO, and it exhibited excellent catalytic performance in the NITRR process. At − 0.45 V vs. RHE, this catalyst achieved a Faraday efficiency of 95.7 % and an ammonia yield of 0.85 mg h−1 cm−2. Further experiments and theoretical calculations demonstrate that the presence of NiO in Cu@NiO/NF stabilizes Cuδ+, thereby enhancing the charge transfer rate and promoting the formation of hydrogen radicals (H•). This work has pioneered a new avenue for the development of efficient and innovative NTIRR materials.
地下水硝态氮（NO3−）污染已成为全球关注的紧迫环境问题。化肥的过量施用是造成这一污染的主要原因，硝酸盐离子对人类健康和生态环境造成重大威胁。电化学还原NO3−为NH3 （NITRR）是氮回收和循环利用的有效途径。在众多电极材料中，铜基催化剂因其低廉的成本和较强的NO3−转化能力而被认为是有前途的。然而，过强的吸附会导致催化剂失活，从而降低催化活性。在本研究中，我们通过Cu和NiO的结合，开发了一种低价铜（Cuδ+）电极材料（Cu@NiO/NF），该材料在NITRR过程中表现出优异的催化性能。在−0.45 V vs. RHE条件下，该催化剂的法拉第效率为95.7%，氨收率为0.85 mg h−1 cm−2。进一步的实验和理论计算表明，Cu@NiO/NF中NiO的存在可以稳定Cuδ+，从而提高电荷转移速率，促进氢自由基（H•）的形成。这项工作为开发高效和创新的NTIRR材料开辟了新的途径。
{"title":"Synergistic integration of nickel oxide and low-valent copper for enhanced electrocatalytic nitrate reduction to ammonia","authors":"Fengjiao Quan , Pengfei Xu , Xiufan Liu , Wenjuan Shen , Yuhao Li , Jianfen Li , Yun He , Fangyuan Chen","doi":"10.1016/j.jiec.2025.07.049","DOIUrl":"10.1016/j.jiec.2025.07.049","url":null,"abstract":"<div><div>Nitrate (NO<sub>3</sub><sup>−</sup>) pollution in groundwater has emerged as a pressing environmental issue of global concern. The excessive application of chemical fertilizers is widely recognized as the primary contributor to this pollution Nitrate ions pose significant risks to human health and the ecological environment. Electrochemical reduction of NO<sub>3</sub><sup>−</sup> to NH<sub>3</sub> (NITRR) represents an effective approach for nitrogen recovery and recycling. Among many electrode materials, copper-based catalysts were considered promising due to their low cost and strong NO<sub>3</sub><sup>−</sup> conversion capability. However, excessively strong adsorption can lead to catalyst deactivation, thereby diminishing catalytic activity. In this study, we developed an electrode material (Cu@NiO/NF) with low-valent copper (Cu<sup>δ+</sup>) through the combination of Cu and NiO, and it exhibited excellent catalytic performance in the NITRR process. At − 0.45 V vs. RHE, this catalyst achieved a Faraday efficiency of 95.7 % and an ammonia yield of 0.85 mg h<sup>−1</sup> cm<sup>−2</sup>. Further experiments and theoretical calculations demonstrate that the presence of NiO in Cu@NiO/NF stabilizes Cu<sup>δ+</sup>, thereby enhancing the charge transfer rate and promoting the formation of hydrogen radicals (H•). This work has pioneered a new avenue for the development of efficient and innovative NTIRR materials.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 387-395"},"PeriodicalIF":5.9,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147083","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}
Pub Date : 2025-07-22DOI: 10.1016/j.jiec.2025.07.010
Raquel Leal Silvério , Pedro M. Portugal , Rodrigo G. Amorim , Diego Pereira Sangi , Gabriel Rodrigues Antunes , Lilian Weitzel Coelho , Ravindra Pandey , Elivelton Alves Ferreira
To safeguard carbon steel during industrial acid pickling, it is essential to create corrosion and atomic hydrogen embrittlement inhibitors that are effective, non-toxic, and easily produced. Here, we synthesized and investigated the efficacy of 2-(nitromethylene)-1,3-oxazinane (NOX) and 2-(nitromethylene)hexahydropyrimidine (NHE) as corrosion inhibitors for SAE 1020 steel in 1.0 mol L−1 HCl aqueous solutions, within a concentration range of 3.7 mmol L−1 to 4.0 mmol L−1. For both inhibitors were obtained, an efficiency up to 82.7% (91.5%) for NHE (NOX), respectively. The NOX compound exhibited a 42.80% inhibitory efficacy of atomic hydrogen permeation. An anomalous behavior was noted in NOX, depending on its concentrations, leading to efficiency reduction. Theoretical calculations were performed using Density Functional Theory (DFT), where it was demonstrated that NOX is an energetically preferable molecule and has smaller binding energy compared with NHE. Two distinct concentrations of NOX molecules were examined, and at a higher concentration, an oxygen atom is released from the molecule and binds to the Fe surface. This phenomenon does not occur at low concentrations, and is ascribed to the anomalous behavior of the NOX molecule. Our finding paves the way for novel and high-efficiency N-heterocycle inhibitors.
{"title":"High inhibition efficiency and hydrogen permeation for novel N-heterocycles of SAE 1020 in HCl solution","authors":"Raquel Leal Silvério , Pedro M. Portugal , Rodrigo G. Amorim , Diego Pereira Sangi , Gabriel Rodrigues Antunes , Lilian Weitzel Coelho , Ravindra Pandey , Elivelton Alves Ferreira","doi":"10.1016/j.jiec.2025.07.010","DOIUrl":"10.1016/j.jiec.2025.07.010","url":null,"abstract":"<div><div>To safeguard carbon steel during industrial acid pickling, it is essential to create corrosion and atomic hydrogen embrittlement inhibitors that are effective, non-toxic, and easily produced. Here, we synthesized and investigated the efficacy of 2-(nitromethylene)-1,3-oxazinane (NOX) and 2-(nitromethylene)hexahydropyrimidine (NHE) as corrosion inhibitors for SAE 1020 steel in 1.0 mol L<sup>−1</sup> HCl aqueous solutions, within a concentration range of 3.7 mmol L<sup>−1</sup> to 4.0 mmol L<sup>−1</sup>. For both inhibitors were obtained, an efficiency up to 82.7% (91.5%) for NHE (NOX), respectively. The NOX compound exhibited a 42.80% inhibitory efficacy of atomic hydrogen permeation. An anomalous behavior was noted in NOX, depending on its concentrations, leading to efficiency reduction. Theoretical calculations were performed using Density Functional Theory (DFT), where it was demonstrated that NOX is an energetically preferable molecule and has smaller binding energy compared with NHE. Two distinct concentrations of NOX molecules were examined, and at a higher concentration, an oxygen atom is released from the molecule and binds to the Fe surface. This phenomenon does not occur at low concentrations, and is ascribed to the anomalous behavior of the NOX molecule. Our finding paves the way for novel and high-efficiency N-heterocycle inhibitors.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"154 ","pages":"Pages 473-486"},"PeriodicalIF":5.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145924233","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}
Pub Date : 2025-07-22DOI: 10.1016/j.jiec.2025.07.051
Walaa Omer , Hamza El-Hosainy , Haitham M. El-Bery , Maged El-Kemary
Lead-free halide perovskites, particularly Cs2AgBiBr6, have gained attention as promising photocatalysts due to their excellent light absorption and tunable photo-responsive properties. However, their practical application is hindered by poor stability in aqueous media and reduced efficiency in high-water environments, where Cs2AgBiBr6 undergoes self-passivation by forming BiOBr, significantly decreasing its photocatalytic activity when water content exceeds 50 vol%. To overcome these limitations, we in situ coupled Cs2AgBiBr6 nanoplatelets (NPLs) with g-C3N4, forming a stable Cs2AgBiBr6 NPLs@g-C3N4@AgBr ternary composite in water (100 vol%). This nanocomposite demonstrated remarkable stability in water through the formation of AgBr rather than BioBr, as confirmed by various spectroscopic and diffraction techniques. The optimized 1:2 wt% ratio of Cs2AgBiBr6 to g-C3N4 leads to the highest degradation rate of Rhodamine B (RhB) of 0.082 min -1 which was 14 times greater than Cs2AgBiBr6 NPLs, g-C3N4, or AgBr alone, surpassing all previously reported Cs2AgBiBr6-based nanocomposites in both efficiency and stability. Furthermore, the scavenging action of RhB led by the heterojunction photocatalyst resulted in the elimination of 98.3 % of RhB under light. The superior photocatalytic activity of the Cs2AgBiBr6 NPLs@g-C3N4@AgBr ternary composite in aqueous media was confirmed through detailed characterization, which revealed that the formation of a dual S-scheme mechanism significantly enhances interfacial charge separation and transfer, resulting in elevated photocurrent, pronounced photoluminescence quenching, and minimized charge transfer resistance. In addition, this ternary composite exhibited robust environmental stability, preserving its crystallinity and morphology after 6 months of air exposure, while maintaining consistent photocatalytic performance across 4 successive cycles in aqueous conditions. Thus, the present results introduce a novel strategy for stabilizing halide perovskites in high water content, expanding their potential for photocatalytic applications in environmental remediation and sustainable energy solutions.
无铅卤化物钙钛矿，特别是Cs2AgBiBr6，由于其优异的光吸收和可调的光响应特性，作为有前途的光催化剂而受到关注。然而，它们的实际应用受到水介质稳定性差和高水环境效率降低的阻碍，在高水环境中，Cs2AgBiBr6通过形成BiOBr进行自钝化，当含水量超过50 vol%时，其光催化活性显著降低。为了克服这些限制，我们将Cs2AgBiBr6纳米血小板（NPLs）与g-C3N4原位耦合，在水中（100 vol%）形成稳定的Cs2AgBiBr6 NPLs@g-C3N4@AgBr三元复合材料。通过各种光谱和衍射技术证实，这种纳米复合材料通过形成AgBr而不是BioBr在水中表现出显著的稳定性。优化后的Cs2AgBiBr6与g-C3N4的体积比为1:2时，罗丹明B （RhB）的降解率最高，为0.082 min -1，是Cs2AgBiBr6 NPLs、g-C3N4或AgBr单独降解率的14倍，在效率和稳定性方面超过了以往报道的所有基于Cs2AgBiBr6的纳米复合材料。此外，异质结光催化剂对RhB的清除作用可使98.3%的RhB在光照下被清除。通过详细表征，证实了Cs2AgBiBr6 NPLs@g-C3N4@AgBr三元复合材料在水介质中优异的光催化活性，发现双S-scheme机制的形成显著增强了界面电荷分离和转移，导致光电流升高，光致发光猝灭明显，电荷转移阻力最小。此外，这种三元复合材料表现出强大的环境稳定性，在空气暴露6个月后仍保持其结晶度和形态，同时在水环境中连续4次循环保持一致的光催化性能。因此，目前的研究结果介绍了一种稳定高含水量卤化物钙钛矿的新策略，扩大了它们在环境修复和可持续能源解决方案中的光催化应用潜力。
{"title":"Water-stable halide perovskite nanocomposite with dual S-scheme for enhanced photocatalysis","authors":"Walaa Omer , Hamza El-Hosainy , Haitham M. El-Bery , Maged El-Kemary","doi":"10.1016/j.jiec.2025.07.051","DOIUrl":"10.1016/j.jiec.2025.07.051","url":null,"abstract":"<div><div>Lead-free halide perovskites, particularly Cs<sub>2</sub>AgBiBr<sub>6</sub>, have gained attention as promising photocatalysts due to their excellent light absorption and tunable photo-responsive properties. However, their practical application is hindered by poor stability in aqueous media and reduced efficiency in high-water environments, where Cs<sub>2</sub>AgBiBr<sub>6</sub> undergoes self-passivation by forming BiOBr, significantly decreasing its photocatalytic activity when water content exceeds 50 vol%. To overcome these limitations, we in situ coupled Cs<sub>2</sub>AgBiBr<sub>6</sub> nanoplatelets (NPLs) with g-C<sub>3</sub>N<sub>4</sub>, forming a stable Cs<sub>2</sub>AgBiBr<sub>6</sub> NPLs@g-C<sub>3</sub>N<sub>4</sub>@AgBr ternary composite in water (100 vol%). This nanocomposite demonstrated remarkable stability in water through the formation of AgBr rather than BioBr, as confirmed by various spectroscopic and diffraction techniques. The optimized 1:2 wt% ratio of Cs<sub>2</sub>AgBiBr<sub>6</sub> to g-C<sub>3</sub>N<sub>4</sub> leads to the highest degradation rate of Rhodamine B (RhB) of 0.082 min <sup>-1</sup> which was 14 times greater than Cs<sub>2</sub>AgBiBr<sub>6</sub> NPLs, g-C<sub>3</sub>N<sub>4</sub>, or AgBr alone, surpassing all previously reported Cs<sub>2</sub>AgBiBr<sub>6</sub>-based nanocomposites in both efficiency and stability. Furthermore, the scavenging action of RhB led by the heterojunction photocatalyst resulted in the elimination of 98.3 % of RhB under light. The superior photocatalytic activity of the Cs<sub>2</sub>AgBiBr<sub>6</sub> NPLs@g-C<sub>3</sub>N<sub>4</sub>@AgBr ternary composite in aqueous media was confirmed through detailed characterization, which revealed that the formation of a dual S-scheme mechanism significantly enhances interfacial charge separation and transfer, resulting in elevated photocurrent, pronounced photoluminescence quenching, and minimized charge transfer resistance. In addition, this ternary composite exhibited robust environmental stability, preserving its crystallinity and morphology after 6 months of air exposure, while maintaining consistent photocatalytic performance across 4 successive cycles in aqueous conditions. Thus, the present results introduce a novel strategy for stabilizing halide perovskites in high water content, expanding their potential for photocatalytic applications in environmental remediation and sustainable energy solutions.</div></div>","PeriodicalId":363,"journal":{"name":"Journal of Industrial and Engineering Chemistry","volume":"155 ","pages":"Pages 407-419"},"PeriodicalIF":5.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147086","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}
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