Despite advancements in NASICON cathodes, their widespread use in sodium-ion batteries (NIBs) remains limited due to low energy density, durability issues, and the use of scarce transition metals like vanadium. While the NASICON-type NaFe2(PO4)(SO4)2 cathode shows potential in addressing these challenges, it encounters issues with electron transport and Na+ diffusion. To overcome these hurdles, we introduce a novel Al3+-substituted NaFe2(PO4)(SO4)2 (NFAPS) cathode in this study, synthesised by a straightforward solid-state ball-milling method. Herein, Al3+ is strategically incorporated at the Fe site, and MWCNT is added in situ during NFAPS synthesis. The doping reduces the band gap, improves charge mobility, and maintains structural integrity during the Na+ insertion and extraction processes. Further, Al3+ enhances the spin state of Fe by attenuating the energy gap of undoped NFAPS cathodes, resulting in improved electrochemical performance, as evidenced by temperature-dependent magnetization susceptibility (M−T) and electron paramagnetic resonance (EPR) measurements. The optimized cathode, NaFe1.93Al0.07(PO4)(SO4)2 (NFAPS07) delivered a high specific discharge capacity of 124 mAh/g at C/20 (1C = 127 mAh/g), impressive rate capability (93.49 mAh/g at C/5 and 78.85 mAh/g at C/2) and good cycle life even at higher current rates. Ex-situ XRD analysis of NFAPS electrodes at various (de)sodiation voltages shows negligible volume expansion with minimal structural distortion. Further, NFAPS07 exhibits the highest reported energy density of 372 Wh kg−1 among all NASICON-based NaFe2(PO4)(SO4)2 cathode. Both experimental and first-principles studies confirm that enhanced charge migration, electrical conductivity, and lower activation barrier stem from synergistic effects of optimised Al3+ doping in NFAPS. Such multivalent cation-doped NASICONs can be adapted to economically design next-generation high-energy–density NIB.
{"title":"Multivalent cation substitution boosted sodium-ion storage in NASICON-type iron-phospho-sulphate cathodes","authors":"Sharad Dnyanu Pinjari, Ravi Chandra Dutta, Saikumar Parshanaboina, Purandas Mudavath, Subhajit Singha, Deepak Dubal, Xijue Wang, John Bell, Ashok Kumar Nanjundan, Rohit Ranganathan Gaddam","doi":"10.1016/j.cej.2024.157979","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157979","url":null,"abstract":"Despite advancements in NASICON cathodes, their widespread use in sodium-ion batteries (NIBs) remains limited due to low energy density, durability issues, and the use of scarce transition metals like vanadium. While the NASICON-type NaFe<sub>2</sub>(PO<sub>4</sub>)(SO<sub>4</sub>)<sub>2</sub> cathode shows potential in addressing these challenges, it encounters issues with electron transport and Na<sup>+</sup> diffusion. To overcome these hurdles, we introduce a novel Al<sup>3+</sup>-substituted NaFe<sub>2</sub>(PO<sub>4</sub>)(SO<sub>4</sub>)<sub>2</sub> (NFAPS) cathode in this study, synthesised by a straightforward solid-state ball-milling method. Herein, Al<sup>3+</sup> is strategically incorporated at the Fe site, and MWCNT is added in situ during NFAPS synthesis. The doping reduces the band gap, improves charge mobility, and maintains structural integrity during the Na<sup>+</sup> insertion and extraction processes. Further, Al<sup>3+</sup> enhances the spin state of Fe by attenuating the energy gap of undoped NFAPS cathodes, resulting in improved electrochemical performance, as evidenced by temperature-dependent magnetization susceptibility (M−T) and electron paramagnetic resonance (EPR) measurements. The optimized cathode, NaFe<sub>1.93</sub>Al<sub>0.07</sub>(PO<sub>4</sub>)(SO<sub>4</sub>)<sub>2</sub> (NFAPS07) delivered a high specific discharge capacity of 124 mAh/g at C/20 (1C = 127 mAh/g), impressive rate capability (93.49 mAh/g at C/5 and 78.85 mAh/g at C/2) and good cycle life even at higher current rates. Ex-situ XRD analysis of NFAPS electrodes at various (de)sodiation voltages shows negligible volume expansion with minimal structural distortion. Further, NFAPS07 exhibits the highest reported energy density of 372 Wh kg<sup>−1</sup> among all NASICON-based NaFe<sub>2</sub>(PO<sub>4</sub>)(SO<sub>4</sub>)<sub>2</sub> cathode. Both experimental and first-principles studies confirm that enhanced charge migration, electrical conductivity, and lower activation barrier stem from synergistic effects of optimised Al<sup>3+</sup> doping in NFAPS. Such multivalent cation-doped NASICONs can be adapted to economically design next-generation high-energy–density NIB.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"9 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694356","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chronic liver failure (CLF) and chronic renal failure (CRF) lead to toxins accumulation, severely impairing organ functions. To address this challenge, a Janus polyethersulfone (PES)-based architecture integrated dense membrane with porous monolith is developed, pioneering an approach for simultaneous plasma separation and toxins adsorption. The porous monolith, featuring high porosity about 83.3 % and substantial specific surface area about 102.06 m2/g, is prepared using the freezing-induced phase separation (FIPS) technique. The porous monolith is composed of polymer networks of PES and amphiphilic copolymer of poly (vinyl pyrrolidone-co-methyl methacrylate) (VM), as well as activated carbon. Among the various monolith, the PES18VM5C2 exhibits the optimal balance of adsorption and anti-protein adhesion. The PES-VM-incorporated dense membrane with a controlled submicron pore size is constructed atop the PES18VM5C2. The dense membrane effectively blocks hemocytes and the porous monolith efficiently adsorbs toxins. Together, the Janus architecture PES18VM5C2M16 allows over 85 % of bovine serum albumin (BSA) to permeate, showcasing its selective permeability. After being integrated into a custom 3D-printed supporting device, the PES18VM5C2M16 achieves significant clearance in creatinine (67.6 %), uric acid (87.4 %), and bilirubin (89.1 %) during 2-hour plasma adsorption test, with minimal impact on essential plasma components such as total protein, albumin, and cholesterol. This work presents a “Janus Interface Architecture” as next-generation platform for plasma separation and toxins adsorption, offering a promising strategy for wearable artificial liver systems.
{"title":"Janus PES-based architectures integrated dense membrane with porous monolith for simultaneous plasma separation and toxins adsorption","authors":"Hongyu Yin, Zhoujun Wang, Xiang Zhang, Weifeng Zhao, Ran Wei, Changsheng Zhao","doi":"10.1016/j.cej.2024.157944","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157944","url":null,"abstract":"Chronic liver failure (CLF) and chronic renal failure (CRF) lead to toxins accumulation, severely impairing organ functions. To address this challenge, a Janus polyethersulfone (PES)-based architecture integrated dense membrane with porous monolith is developed, pioneering an approach for simultaneous plasma separation and toxins adsorption. The porous monolith, featuring high porosity about 83.3 % and substantial specific surface area about 102.06 m<sup>2</sup>/g, is prepared using the freezing-induced phase separation (FIPS) technique. The porous monolith is composed of polymer networks of PES and amphiphilic copolymer of poly (vinyl pyrrolidone-co-methyl methacrylate) (VM), as well as activated carbon. Among the various monolith, the PES<sub>18</sub>VM<sub>5</sub>C<sub>2</sub> exhibits the optimal balance of adsorption and anti-protein adhesion. The PES-VM-incorporated dense membrane with a controlled submicron pore size is constructed atop the PES<sub>18</sub>VM<sub>5</sub>C<sub>2</sub>. The dense membrane effectively blocks hemocytes and the porous monolith efficiently adsorbs toxins. Together, the Janus architecture PES<sub>18</sub>VM<sub>5</sub>C<sub>2</sub>M<sub>16</sub> allows over 85 % of bovine serum albumin (BSA) to permeate, showcasing its selective permeability. After being integrated into a custom 3D-printed supporting device, the PES<sub>18</sub>VM<sub>5</sub>C<sub>2</sub>M<sub>16</sub> achieves significant clearance in creatinine (67.6 %), uric acid (87.4 %), and bilirubin (89.1 %) during 2-hour plasma adsorption test, with minimal impact on essential plasma components such as total protein, albumin, and cholesterol. This work presents a “Janus Interface Architecture” as next-generation platform for plasma separation and toxins adsorption, offering a promising strategy for wearable artificial liver systems.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"24 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694363","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Quasi-solid-state lithium batteries (QSSLBs) are emerging as attractive candidates for overcoming the disadvantages of liquid and solid batteries. However, they face challenges in terms of enhancing the poor interfacial stability and promoting selective Li+ conduction. Herein, one-stone-for-two-birds strategy is proposed that involves using a two-directional conjugated metal organic framework (2D-cMOF, Fe-TABQ) as both the cathode material and a polymer–electrolyte filler to construct high-performance quasi-solid-state lithium–organic batteries (QSSLOBs). Additionally, Fe-TABQ promotes the cleavage of C–F bonds, thus facilitating the formation of a LiF-rich solid electrolyte interface (SEI). Therefore, the composite polymer electrolyte presents a high Li+ transference number of 0.93 and a high ionic conductivity of 6.22 × 10−3 mS cm−1. Meanwhile, Li/Li symmetric cells deliver stable cyclability for 1,500 h at 25 ℃ and a current density of 0.05 mA cm−2. Even the assembled QSSLOBs exhibit a high initial discharge specific capacity of 248.39 mAh/g at 25 ℃, and 50 mA g−1 and long cycle stability with 70 % capacity retention after 200 cycles at 25 ℃ and 1,000 mA g−1. The present findings reveal the multiple functional potentials of 2D-cMOFs in constructing robust QSSLOBs
{"title":"One-stone-for-two-birds strategy to construct robust 2D conjugated metal-organic framework-based quasi-solid-state lithium-organic batteries","authors":"Jingwen Cao, Xupeng Zhang, Ying Wang, Shuainan Sha, Qiong Wu, Xingwei Sun, Heng-Guo Wang","doi":"10.1016/j.cej.2024.157873","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157873","url":null,"abstract":"Quasi-solid-state lithium batteries (QSSLBs) are emerging as attractive candidates for overcoming the disadvantages of liquid and solid batteries. However, they face challenges in terms of enhancing the poor interfacial stability and promoting selective Li<sup>+</sup> conduction. Herein, one-stone-for-two-birds strategy is proposed that involves using a two-directional conjugated metal organic framework (2D-cMOF, Fe-TABQ) as both the cathode material and a polymer–electrolyte filler to construct high-performance quasi-solid-state lithium–organic batteries (QSSLOBs). Additionally, Fe-TABQ promotes the cleavage of C–F bonds, thus facilitating the formation of a LiF-rich solid electrolyte interface (SEI). Therefore, the composite polymer electrolyte presents a high Li<sup>+</sup> transference number of 0.93 and a high ionic conductivity of 6.22 × 10<sup>−3</sup> mS cm<sup>−1</sup>. Meanwhile, Li/Li symmetric cells deliver stable cyclability for 1,500 h at 25 ℃ and a current density of 0.05 mA cm<sup>−2</sup>. Even the assembled QSSLOBs exhibit a high initial discharge specific capacity of 248.39 mAh/g at 25 ℃, and 50 mA g<sup>−1</sup> and long cycle stability with 70 % capacity retention after 200 cycles at 25 ℃ and 1,000 mA g<sup>−1</sup>. The present findings reveal the multiple functional potentials of 2D-cMOFs in constructing robust QSSLOBs","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"13 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Microbial desalination cells (MDC) are an emerging technology addressing wastewater treatment, energy production, and freshwater scarcity. This research aims to explore plant-derived extracts, rich in polyphenols, as mediators to improve electron transfer in MDCs. Vetiver (Chrysopogon zizanioides) and onion (Allium cepa) peel extracts were tested at different concentrations using Shewanella putrefaciens MTCC 8104 and mixed cultures as exoelectrogens. The results revealed that onion peel extract (100 µg/mL) with a mixed culture (OM-MDC) achieved the highest power density of 38.27 ± 0.7 mW/m2, a 2.7-fold increase compared to controls. COD removal reached 99.2 ± 0.2 % in the vetiver-mediated mixed culture system (VM-MDC). Real-time brackish water treatment at optimized mediator concentration with OM-MDC showcased a power density of 26.85 ± 0.5 mW/m2. The electrochemical analysis demonstrated a significant decrease in internal resistance and an improved expression of oxidation and reduction potentials following the addition of the mediator. Overall, plant extracts proved effective, sustainable alternatives to synthetic mediators, demonstrating potential for practical applications in seawater and brackish water treatment.
{"title":"Impact of plant-derived electron shuttles on the exoelectrogens for enhanced novel microbial desalination cell performance","authors":"Sandhya Prakash, Samsudeen Naina Mohamed, Kalaichelvi Ponnusamy","doi":"10.1016/j.cej.2024.157886","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157886","url":null,"abstract":"Microbial desalination cells (MDC) are an emerging technology addressing wastewater treatment, energy production, and freshwater scarcity. This research aims to explore plant-derived extracts, rich in polyphenols, as mediators to improve electron transfer in MDCs. Vetiver (<em>Chrysopogon zizanioides)</em> and onion (<em>Allium cepa)</em> peel extracts were tested at different concentrations using <em>Shewanella putrefaciens</em> MTCC 8104 and mixed cultures as exoelectrogens. The results revealed that onion peel extract (100 µg/mL) with a mixed culture (OM-MDC) achieved the highest power density of 38.27 ± 0.7 mW/m<sup>2</sup>, a 2.7-fold increase compared to controls. COD removal reached 99.2 ± 0.2 % in the vetiver-mediated mixed culture system (VM-MDC). Real-time brackish water treatment at optimized mediator concentration with OM-MDC showcased a power density of 26.85 ± 0.5 mW/m<sup>2</sup>. The electrochemical analysis demonstrated a significant decrease in internal resistance and an improved expression of oxidation and reduction potentials following the addition of the mediator. Overall, plant extracts proved effective, sustainable alternatives to synthetic mediators, demonstrating potential for practical applications in seawater and brackish water treatment.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"18 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Natural hydrogels like gelatin are ideal for fabricating sensors that monitor human body signals due to their excellent biocompatibility. However, their typically large molecular weight restricts molecular mobility and repositioning under stress, limiting their stretchability performance. In this study, a hydrogel sensor PAM-Gel/β-GP/LiCl (named: PGBL) combining gelatin with ion-complexation, is proposed. Through the synergistic effect of sodium β-glycerophosphate (β-GP) and LiCl, the PAM-gelatin-based hydrogel achieves an extraordinary elongation strain exceeding 11000 %, enabling ultra-stretchability. Additionally, PGBL exhibits excellent electrical conductivity (8.2 S/m), high sensitivity (GF approximately 4.1), and resilience to low temperatures (−24 °C). Moreover, PGBL demonstrates strong adhesion, making it suitable for skin attachment in human body sensing applications. Integrating PGBL hydrogel sensors with a robotic hand has led to the development of a human–machine interaction control system. Furthermore, combining real-time data transmission and visualization technologies has resulted in a real-time respiratory monitoring system, which can monitor sleep apnoea blockage. PGBL hydrogel sensors show promising applications in biomedical fields and biosensing, highlighting their potential in healthcare monitoring systems.
{"title":"High-performance gelatin-based hydrogel flexible sensor for respiratory monitoring and human–machine interaction","authors":"Ruonan Liu, Yanpeng Wang, Haoxiang Chu, Yiqi Li, Yehan Li, Yunjun Zhao, Ye Tian, Zhixiu Xia","doi":"10.1016/j.cej.2024.157975","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157975","url":null,"abstract":"Natural hydrogels like gelatin are ideal for fabricating sensors that monitor human body signals due to their excellent biocompatibility. However, their typically large molecular weight restricts molecular mobility and repositioning under stress, limiting their stretchability performance. In this study, a hydrogel sensor PAM-Gel/β-GP/LiCl (named: PGBL) combining gelatin with ion-complexation, is proposed. Through the synergistic effect of sodium β-glycerophosphate (β-GP) and LiCl, the PAM-gelatin-based hydrogel achieves an extraordinary elongation strain exceeding 11000 %, enabling ultra-stretchability. Additionally, PGBL exhibits excellent electrical conductivity (8.2 S/m), high sensitivity (GF approximately 4.1), and resilience to low temperatures (−24 °C). Moreover, PGBL demonstrates strong adhesion, making it suitable for skin attachment in human body sensing applications. Integrating PGBL hydrogel sensors with a robotic hand has led to the development of a human–machine interaction control system. Furthermore, combining real-time data transmission and visualization technologies has resulted in a real-time respiratory monitoring system, which can monitor sleep apnoea blockage. PGBL hydrogel sensors show promising applications in biomedical fields and biosensing, highlighting their potential in healthcare monitoring systems.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"36 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142690605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Endocrine disrupting chemicals (EDCs) interfere with the normal secretion, transport and metabolism of human hormones, thus affecting neurological, reproductive and immune functions. Photocatalysis is regarded as a facile organic degradation technique. The construction of heterojunctions can modulate the reactive oxygen species and enhance the photocatalytic performance of semiconductors. However, poor contact interfaces still severely limit carrier separation and transfer. Herein we have doped Co to modulate the band structure of Bi2O2CO3 while facilitating the in situ growth of BiOI on its surface via shared Bi atoms. This approach led to the development of a 2D/2D Co-Bi2O2CO3/BiOI (Co-BOC/BiOI) S-scheme heterojunction characterized by atomically close contact interfaces. Furthermore, the photo-electrochemical characterization results indicate that the light adsorption capacity, carrier separation and transport efficiency of the optimized Co-BOC/BiOI-3 are greatly improved. This system demonstrates almost 100% removal rate for three typical EDCs within 60 min. The degradation kinetic constants show an improvement by an order of magnitude compared to single BiOI and Bi2O2CO3. More importantly, O2•﹣, which is produced from O2 reduction on high negative conduction band, can be subsequently oxidized into 1O2 by photogenerated hole. Electron paramagnetic resonance and quenching experiments indicate that the organics degradation process is dominated by 1O2. This work offers new insights into the construction of high-quality S-scheme heterojunction interfaces for modulation of reactive oxygen species.
干扰内分泌的化学物质（EDCs）会干扰人体激素的正常分泌、运输和代谢，从而影响神经、生殖和免疫功能。光催化被认为是一种简便的有机降解技术。异质结的构建可以调节活性氧，提高半导体的光催化性能。然而，不良的接触界面仍然严重限制了载流子的分离和转移。在此，我们通过掺杂 Co 来调节 Bi2O2CO3 的带状结构，同时通过共享 Bi 原子促进 BiOI 在其表面的原位生长。通过这种方法，我们开发出了一种二维/二维 Co-Bi2O2CO3/BiOI （Co-BOC/BiOI）S 型异质结，其特点是原子紧密接触界面。此外，光电化学特性分析结果表明，优化后的 Co-BOC/BiOI-3 的光吸附能力、载流子分离和传输效率都得到了大幅提高。该系统在 60 分钟内对三种典型 EDC 的去除率几乎达到 100%。与单一 BiOI 和 Bi2O2CO3 相比，降解动力学常数提高了一个数量级。更重要的是，高负导带上的 O2 还原产生的 O2--可被光生空穴氧化成 1O2。电子顺磁共振和淬灭实验表明，有机物降解过程主要由 1O2 主导。这项工作为构建用于调节活性氧的高质量 S 型异质结界面提供了新的见解。
{"title":"Bi atom sharing Co-Bi2O2CO3/BiOI S-scheme induced singlet oxygen-dominated photocatalytic oxidation system","authors":"Zhiang Hou, Jinzhu Yue, Hao Chen, Jinnan Wang, Aimin Li, Philippe François-Xavier Corvini","doi":"10.1016/j.cej.2024.157963","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157963","url":null,"abstract":"Endocrine disrupting chemicals (EDCs) interfere with the normal secretion, transport and metabolism of human hormones, thus affecting neurological, reproductive and immune functions. Photocatalysis is regarded as a facile organic degradation technique. The construction of heterojunctions can modulate the reactive oxygen species and enhance the photocatalytic performance of semiconductors. However, poor contact interfaces still severely limit carrier separation and transfer. Herein we have doped Co to modulate the band structure of Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> while facilitating the in situ growth of BiOI on its surface via shared Bi atoms. This approach led to the development of a 2D/2D Co-Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>/BiOI (Co-BOC/BiOI) S-scheme heterojunction characterized by atomically close contact interfaces. Furthermore, the photo-electrochemical characterization results indicate that the light adsorption capacity, carrier separation and transport efficiency of the optimized Co-BOC/BiOI-3 are greatly improved. This system demonstrates almost 100% removal rate for three typical EDCs within 60 min. The degradation kinetic constants show an improvement by an order of magnitude compared to single BiOI and Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>. More importantly, O<sub>2</sub><sup>•﹣</sup>, which is produced from O<sub>2</sub> reduction on high negative conduction band, can be subsequently oxidized into <sup>1</sup>O<sub>2</sub> by photogenerated hole. Electron paramagnetic resonance and quenching experiments indicate that the organics degradation process is dominated by <sup>1</sup>O<sub>2</sub>. This work offers new insights into the construction of high-quality S-scheme heterojunction interfaces for modulation of reactive oxygen species.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"4 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142690651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
212Pb/212Bi hold significant potential for targeted cancer therapy; however, their supply remains severely limited. The extraction of 212Pb/212Bi from natural thorium is expected to fundamentally address this issue. This study proposes and verifies a new, efficient and low-cost method for separating 212Pb/212Bi from natural 232Th by investigating the separation behavior and mechanism of a silica-supported anion exchange resin (SiPyR-N4) toward multiple types of metal cations in hydrochloric solution. The experimental results demonstrated that SiPyR-N4 was successfully prepared with a uniform shape, porous structure, and containing quaternary amines. SiPyR-N4 showed extremely high selectivity for Pb2+ and Bi3+, but no affinity for Th4+, La3+, and Ba2+. The adsorption speed was more than six times as fast as traditional resins, providing significant advantages in the separation of short-lived nuclides. The hot separation experiment suggested that 212Pb and 212Bi were successfully isolated from natural 232Th by using natural thorium as the raw material, and the long-lived nuclides were removed completely. The selective separation mechanism was attributed to Pb2+ and Bi3+ forming anionic complexes in the hydrochloric acid medium, while Th4+, Ra2+, and Ac3+ did not form such complexes. Pb2+ and Bi3+ were bound to the active sites via chloride bridges, with [PbCl3]− and [BiCl6]3− serving as the main adsorbed species. This study is the first to report the direct and selective separation of 212Pb and 212Bi from 232Th decay chains using non-crown ether materials, and it provides an excellent material candidate for the separation of short-lived nuclides, showing significant application potential in the future.
{"title":"An advanced separation method for the acquisition of 212Pb/212Bi from natural thorium","authors":"Xuexiang He, Wannian Feng, Zhuo Wang, Shunyan Ning, Lidan Lv, Lifeng Chen, Wenlong Li, Xiangbiao Yin, Yuezhou Wei, Hiroshi Watabe","doi":"10.1016/j.cej.2024.157971","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157971","url":null,"abstract":"<sup>212</sup>Pb/<sup>212</sup>Bi hold significant potential for targeted cancer therapy; however, their supply remains severely limited. The extraction of <sup>212</sup>Pb/<sup>212</sup>Bi from natural thorium is expected to fundamentally address this issue. This study proposes and verifies a new, efficient and low-cost method for separating <sup>212</sup>Pb/<sup>212</sup>Bi from natural <sup>232</sup>Th by investigating the separation behavior and mechanism of a silica-supported anion exchange resin (SiPyR-N4) toward multiple types of metal cations in hydrochloric solution. The experimental results demonstrated that SiPyR-N4 was successfully prepared with a uniform shape, porous structure, and containing quaternary amines. SiPyR-N4 showed extremely high selectivity for Pb<sup>2+</sup> and Bi<sup>3+</sup>, but no affinity for Th<sup>4+</sup>, La<sup>3+</sup>, and Ba<sup>2+</sup>. The adsorption speed was more than six times as fast as traditional resins, providing significant advantages in the separation of short-lived nuclides. The hot separation experiment suggested that <sup>212</sup>Pb and <sup>212</sup>Bi were successfully isolated from natural <sup>232</sup>Th by using natural thorium as the raw material, and the long-lived nuclides were removed completely. The selective separation mechanism was attributed to Pb<sup>2+</sup> and Bi<sup>3+</sup> forming anionic complexes in the hydrochloric acid medium, while Th<sup>4+</sup>, Ra<sup>2+</sup>, and Ac<sup>3+</sup> did not form such complexes. Pb<sup>2+</sup> and Bi<sup>3+</sup> were bound to the active sites via chloride bridges, with [PbCl<sub>3</sub>]<sup>−</sup> and [BiCl<sub>6</sub>]<sup>3−</sup> serving as the main adsorbed species. This study is the first to report the direct and selective separation of <sup>212</sup>Pb and <sup>212</sup>Bi from <sup>232</sup>Th decay chains using non-crown ether materials, and it provides an excellent material candidate for the separation of short-lived nuclides, showing significant application potential in the future.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"255 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142690603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 : 2024-11-23DOI: 10.1016/j.cej.2024.157918
Sijing Yao, Jianqing Ma, Di Ma, Mika Erik Tapio Sillanpää, Minghua Zhou, Qing Ye, Huixia Jin, Kefeng Zhang
Chromium, as a widely utilized transition metal, presents wastewater with high toxicity and challenging treatment. To date, there has been limited exploration regarding the application of chromium in homogeneous Fenton-like reactions. This study aims to explore the potential of Cr(VI) and Cr(III) to activate hydrogen peroxide (H2O2) and permonosulfate (PMS) for degrading coexisting pollutants in homogeneous solutions. The Cr(VI)/PMS system was found to be the most effective, with a 95.58 % removal efficiency for the azo dye Acid Red 73 (AR73). The Cr(VI)/H2O2 system followed with 72.35 %, while the Cr(III)/H2O2 and Cr(III)/PMS systems showed lower efficiencies at 25.65 % and 16.95 %, respectively. Various techniques were employed to delve into the mechanisms underlying chromium activation. The results indicate that both Cr(VI) and Cr(III) can activate H2O2 to generate hydroxyl radical (HO•). Moreover, Cr(VI) can activate PMS in the pH range of 3 ∼ 11, producing HO•, sulfate radical (SO•- 4), and singlet oxygen (1O2), while Cr(III) engages in chelation with PMS, causing the reaction to cease. Additionally, this study reveals that the chelating agent EDTA, upon complexing with Cr(III), efficiently activates PMS to generate 1O2, and the mechanism behind EDTA-Cr(III) activation of PMS was elucidated through DFT calculations. An integrated evaluation of Cr performance in the Fenton-like reaction provides new research directions for the removal of pollutants from chromium-containing wastewater.
{"title":"Comprehensive evaluation and Mechanistic comparison of Cr-Catalyzed homogeneous Fenton-Like reactions for coexisting organics degradation","authors":"Sijing Yao, Jianqing Ma, Di Ma, Mika Erik Tapio Sillanpää, Minghua Zhou, Qing Ye, Huixia Jin, Kefeng Zhang","doi":"10.1016/j.cej.2024.157918","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157918","url":null,"abstract":"Chromium, as a widely utilized transition metal, presents wastewater with high toxicity and challenging treatment. To date, there has been limited exploration regarding the application of chromium in homogeneous Fenton-like reactions. This study aims to explore the potential of Cr(VI) and Cr(III) to activate hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and permonosulfate (PMS) for degrading coexisting pollutants in homogeneous solutions. The Cr(VI)/PMS system was found to be the most effective, with a 95.58 % removal efficiency for the azo dye Acid Red 73 (AR73). The Cr(VI)/H<sub>2</sub>O<sub>2</sub> system followed with 72.35 %, while the Cr(III)/H<sub>2</sub>O<sub>2</sub> and Cr(III)/PMS systems showed lower efficiencies at 25.65 % and 16.95 %, respectively. Various techniques were employed to delve into the mechanisms underlying chromium activation. The results indicate that both Cr(VI) and Cr(III) can activate H<sub>2</sub>O<sub>2</sub> to generate hydroxyl radical (HO<sup>•</sup>). Moreover, Cr(VI) can activate PMS in the pH range of 3 ∼ 11, producing HO<sup>•</sup>, sulfate radical (SO•- 4), and singlet oxygen (<sup>1</sup>O<sub>2</sub>), while Cr(III) engages in chelation with PMS, causing the reaction to cease. Additionally, this study reveals that the chelating agent EDTA, upon complexing with Cr(III), efficiently activates PMS to generate <sup>1</sup>O<sub>2</sub>, and the mechanism behind EDTA-Cr(III) activation of PMS was elucidated through DFT calculations. An integrated evaluation of Cr performance in the Fenton-like reaction provides new research directions for the removal of pollutants from chromium-containing wastewater.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"184 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 : 2024-11-23DOI: 10.1016/j.cej.2024.157976
Ganapaty Manickavasagam, Chao He, Tao Zhou, Kun-Yi Andrew Lin, Tuan Sherwyn Hamidon, M. Hazwan Hussin, Mardiana Saaid, Wen-Da Oh
The exploration of waste-derived hydrochar as peroxymonosulfate (PMS) activator for fluoroquinolones removal remains limited. Herein, various Co, N-co-doped hydrochars (Co-N-HCs) were designed via different fabrication pathways (i.e., one-, two-, and three-step pathways) and their characteristics were investigated, revealing the variation in surface chemistry due to different fabrication approaches. These Co-N-HCs with different surface chemistry were employed to remove fluoroquinolone antibiotics, namely ciprofloxacin (CIP), via PMS activation and the results show that the performance of one-step catalyst (HC-1S-A-2) was the highest with kapp = 0.026 min−1 compared to the two-step and three-step catalysts (0.008 – 0.022 min−1). The better performance of the HC-1S-A-2 was due to its highest ID/IG ratio (2.20) and relatively higher electronic conductivity (6.21 × 10-4 S m−1) of the catalyst, which could enhance the PMS activation and reactive species (RS) generation for CIP removal. The catalyst was further optimized by varying Co content, and the 2.0 wt% Co content (HC-1S-A-3) emerged as the most effective, demonstrating efficient CIP removal across various operational conditions. The chemical scavenging and electrochemical studies revealed that the hydroxyl radical (major ROS), sulfate radical, singlet oxygen, and other nonradical pathways were involved in CIP degradation while the major active site was Co coupled with pyrrolic N and pyridinic N. Additionally, based on the identified CIP intermediates during the degradation process, the CIP degradation pathways were proposed, and the intermediates were subjected to a toxicity assessment. The results showed that CIP and its intermediates can be successfully mineralized and detoxified by increasing the catalytic reaction time. Overall, this work provides a sustainable approach to transform waste into engineered hydrochar for pollutants removal.
将废物衍生水煤浆作为过一硫酸盐（PMS）活化剂用于去除氟喹诺酮类药物的探索仍然有限。本文通过不同的制备途径（即一步法、二步法和三步法）设计了各种掺杂 Co、N 的水碳（Co-N-HCs），并研究了它们的特性，揭示了不同制备方法导致的表面化学变化。结果表明，与两步法和三步法催化剂（0.008 - 0.022 min-1）相比，一步法催化剂（HC-1S-A-2）的性能最高，kapp = 0.026 min-1。HC-1S-A-2 催化剂性能更好的原因在于其最高的内径/内径比（2.20）和相对较高的电子电导率（6.21 × 10-4 S m-1），这可以增强 PMS 的活化和反应物（RS）的生成，从而去除 CIP。通过改变 Co 含量对催化剂进行了进一步优化，2.0 wt% Co 含量（HC-1S-A-3）的催化剂最为有效，在各种操作条件下都能高效去除 CIP。化学清除和电化学研究表明，羟基自由基（主要的 ROS）、硫酸根自由基、单线态氧和其他非自由基途径参与了 CIP 降解，而主要的活性位点是 Co 与吡咯烷 N 和吡啶 N 的偶联。结果表明，通过增加催化反应时间，CIP 及其中间产物可以成功矿化和解毒。总之，这项工作提供了一种可持续的方法，将废物转化为工程水炭，用于去除污染物。
{"title":"Insights into the sustainable design of engineered hydrochar co-doped with cobalt and nitrogen as peroxymonosulfate activator for fluoroquinolones removal","authors":"Ganapaty Manickavasagam, Chao He, Tao Zhou, Kun-Yi Andrew Lin, Tuan Sherwyn Hamidon, M. Hazwan Hussin, Mardiana Saaid, Wen-Da Oh","doi":"10.1016/j.cej.2024.157976","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157976","url":null,"abstract":"The exploration of waste-derived hydrochar as peroxymonosulfate (PMS) activator for fluoroquinolones removal remains limited. Herein, various Co, N-co-doped hydrochars (Co-N-HCs) were designed via different fabrication pathways (i.e., one-, two-, and three-step pathways) and their characteristics were investigated, revealing the variation in surface chemistry due to different fabrication approaches. These Co-N-HCs with different surface chemistry were employed to remove fluoroquinolone antibiotics, namely ciprofloxacin (CIP), via PMS activation and the results show that the performance of one-step catalyst (HC-1S-A-2) was the highest with <em>k<sub>app</sub></em> = 0.026 min<sup>−1</sup> compared to the two-step and three-step catalysts (0.008 – 0.022 min<sup>−1</sup>). The better performance of the HC-1S-A-2 was due to its highest I<sub>D</sub>/I<sub>G</sub> ratio (2.20) and relatively higher electronic conductivity (6.21 × 10<sup>-4</sup> S m<sup>−1</sup>) of the catalyst, which could enhance the PMS activation and reactive species (RS) generation for CIP removal. The catalyst was further optimized by varying Co content, and the 2.0 wt% Co content (HC-1S-A-3) emerged as the most effective, demonstrating efficient CIP removal across various operational conditions. The chemical scavenging and electrochemical studies revealed that the hydroxyl radical (major ROS), sulfate radical, singlet oxygen, and other nonradical pathways were involved in CIP degradation while the major active site was Co coupled with pyrrolic N and pyridinic N. Additionally, based on the identified CIP intermediates during the degradation process, the CIP degradation pathways were proposed, and the intermediates were subjected to a toxicity assessment. The results showed that CIP and its intermediates can be successfully mineralized and detoxified by increasing the catalytic reaction time. Overall, this work provides a sustainable approach to transform waste into engineered hydrochar for pollutants removal.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"15 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 : 2024-11-23DOI: 10.1016/j.cej.2024.157988
Min Wang, Guorong Xu, Yingzhen Wu, Ralph Rolly Gonzales, Ke Xu, Heli Zhao, Fenfen Wang
Interfacial solar evaporation has emerged as a promising technology for sustainable freshwater production using renewable green energy to alleviate freshwater shortages. Hydrogels have been regarded as the most effective platform materials for interfacial solar evaporation due to their inherent hydrophilicity and water retention capabilities. This review initially describes the endeavors in molecular and structural engineering of hydrogels to achieve highly efficient interfacial solar evaporation with increased intermediated water content, improved heat confinement and water transport management, salt-resilience and three-dimensional structures. Subsequently, it scrutinizes and discusses the development of hydrogel evaporators with additional functionalities, including stimuli-responsive properties, self-healing, recyclability, disinfection, and volatile organic compound removal abilities for better water purification performance. Furthermore, it summarizes the potential applications of hydrogels in the emerging next-generation interfacial solar evaporators for metal ion extraction, electricity generation, and evaporative cooling beyond seawater desalination. Finally, conclusions are drawn and future perspectives on hydrogel-based systems are proposed. This review will provide insights into engineering hydrogels for achieving highly efficient solar evaporation performance while promoting practical and wide-ranging applications.
{"title":"Engineering hydrogels towards next-generation multi-functional interfacial solar evaporators beyond seawater desalination","authors":"Min Wang, Guorong Xu, Yingzhen Wu, Ralph Rolly Gonzales, Ke Xu, Heli Zhao, Fenfen Wang","doi":"10.1016/j.cej.2024.157988","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157988","url":null,"abstract":"Interfacial solar evaporation has emerged as a promising technology for sustainable freshwater production using renewable green energy to alleviate freshwater shortages. Hydrogels have been regarded as the most effective platform materials for interfacial solar evaporation due to their inherent hydrophilicity and water retention capabilities. This review initially describes the endeavors in molecular and structural engineering of hydrogels to achieve highly efficient interfacial solar evaporation with increased intermediated water content, improved heat confinement and water transport management, salt-resilience and three-dimensional structures. Subsequently, it scrutinizes and discusses the development of hydrogel evaporators with additional functionalities, including stimuli-responsive properties, self-healing, recyclability, disinfection, and volatile organic compound removal abilities for better water purification performance. Furthermore, it summarizes the potential applications of hydrogels in the emerging next-generation interfacial solar evaporators for metal ion extraction, electricity generation, and evaporative cooling beyond seawater desalination. Finally, conclusions are drawn and future perspectives on hydrogel-based systems are proposed. This review will provide insights into engineering hydrogels for achieving highly efficient solar evaporation performance while promoting practical and wide-ranging applications.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"18 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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