Room temperature phosphorescence (RTP) materials exhibit fascinating optical properties with great potential for various applications in the fields of luminescent displays and information encryption. However, most afterglow materials rely on pre-processing techniques such as molding and inkjet printing, greatly limiting the portability of their applications. In this study, we propose a reversible photoactivated phosphorescent anti-counterfeiting material. A dynamic photo-printable afterglow film that can be naturally erased was developed by doping carbon dots (CDs) of ofloxacin into polylactic acid (PLA). The material exhibits a 15 s yellow-to-green dynamic afterglow, while the lifetime of the material jumps from 2.5 ms to a maximum of 625 ms under continuous UV irradiation for less than 60 s. Characterization results showed that dynamic RTP originated from external oxygen-containing functional groups and internal nitrogen heterocycles with different decay rates within CDs. Further studies suggested that photoactivation properties should be attributed to the highly oxygen permeable but UV responsive structure of PLA. While oxygen in the membrane was excited by UV light, cross-linking occurs between PLA molecules, providing a rigid environment for CDs and limiting the subsequent entry of oxygen, further extending its lifetime. Based on the above advantages, this dynamic afterglow material has been successfully applied in light-emitting displays and optical molecular logic operation unit design.
室温磷光（RTP）材料展现出迷人的光学特性，在发光显示和信息加密领域具有巨大的应用潜力。然而，大多数余辉材料都依赖于成型和喷墨打印等预处理技术，大大限制了其应用的便携性。在这项研究中，我们提出了一种可逆光激活磷光防伪材料。通过在聚乳酸（PLA）中掺入氧氟沙星碳点（CD），我们开发出了一种可自然擦除的动态光打印余辉膜。该材料显示出 15 秒的黄绿色动态余辉，而在连续紫外线照射不到 60 秒的情况下，材料的寿命从 2.5 毫秒跃升至最大 625 毫秒。表征结果表明，动态 RTP 源自外部含氧官能团和内部氮杂环，它们在光盘中的衰减速度不同。进一步的研究表明，光活化特性应归因于聚乳酸的高透氧性和紫外线响应结构。当膜中的氧气被紫外线激发时，聚乳酸分子之间会发生交联，从而为 CD 提供了一个刚性环境，并限制了氧气的后续进入，进一步延长了 CD 的使用寿命。基于上述优点，这种动态余辉材料已成功应用于发光显示器和光学分子逻辑运算单元设计中。
{"title":"Time-dependent phosphorescence from carbon dots enables multidimensional photoactivated printing and tunable molecular calculations","authors":"Jianwen Zeng, Zhaorun Tang, Junping Yin, Zhihao Guan, Ruyi Wei, Xianwen Ke, Xinghai Liu","doi":"10.1016/j.cej.2024.157819","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157819","url":null,"abstract":"Room temperature phosphorescence (RTP) materials exhibit fascinating optical properties with great potential for various applications in the fields of luminescent displays and information encryption. However, most afterglow materials rely on pre-processing techniques such as molding and inkjet printing, greatly limiting the portability of their applications. In this study, we propose a reversible photoactivated phosphorescent anti-counterfeiting material. A dynamic photo-printable afterglow film that can be naturally erased was developed by doping carbon dots (CDs) of ofloxacin into polylactic acid (PLA). The material exhibits a 15 s yellow-to-green dynamic afterglow, while the lifetime of the material jumps from 2.5 ms to a maximum of 625 ms under continuous UV irradiation for less than 60 s. Characterization results showed that dynamic RTP originated from external oxygen-containing functional groups and internal nitrogen heterocycles with different decay rates within CDs. Further studies suggested that photoactivation properties should be attributed to the highly oxygen permeable but UV responsive structure of PLA. While oxygen in the membrane was excited by UV light, cross-linking occurs between PLA molecules, providing a rigid environment for CDs and limiting the subsequent entry of oxygen, further extending its lifetime. Based on the above advantages, this dynamic afterglow material has been successfully applied in light-emitting displays and optical molecular logic operation unit design.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"33 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671082","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}
Polyimide (PI) foams possess excellent mechanical properties and high-temperature resistance, which present significant utility in the aerospace, transportation, and microelectronics industries. The microstructure of PI foam, specifically the pore size and porosity, significantly influences its physical and mechanical properties. However, achieving both high porosity and small pore size simultaneously is greatly challenging for PI foams, especially via the foaming method. Here, we report PI foams with mean pore size of 98.1 μm and porosity of 92 % using a one-step scrape foaming method. The scraping thickness is found to be key to adjusting the pore size of the foam due to the interface effect in the initial stage, and maintaining optimal air pressure and low temperature allows slow bubble growth without bursting or merging, resulting in PI foams with high porosity and small pore size. The PI foam we fabricated exhibits excellent thermal insulating performance, with a low thermal conductivity of 20 mW/m∙K. The scrape foaming method provides an efficient and low-cost strategy for the preparation of PI foams with a tunable porous structure and is expected to find a variety of applications in thermal insulation and environmental protection.
聚酰亚胺（PI）泡沫具有优异的机械性能和耐高温性能，在航空航天、交通运输和微电子行业具有重要用途。聚酰亚胺泡沫的微观结构，特别是孔径和孔隙率，对其物理和机械性能有重大影响。然而，同时实现高孔隙率和小孔径对于 PI 泡沫来说是一项巨大的挑战，尤其是通过发泡方法。在此，我们报告了采用一步刮削发泡法获得的平均孔径为 98.1 μm、孔隙率为 92 % 的聚氨酯泡沫。我们发现，由于初始阶段的界面效应，刮削厚度是调整泡沫孔径的关键，而保持最佳气压和低温可使气泡缓慢生长，不会破裂或合并，从而产生孔隙率高、孔径小的聚氨酯泡沫。我们制造的 PI 泡沫具有出色的隔热性能，导热系数低至 20 mW/m∙K。刮削发泡法为制备具有可调多孔结构的聚氨酯泡沫提供了一种高效、低成本的策略，有望在隔热和环保领域得到广泛应用。
{"title":"Polyimide foams with high porosity in the micrometer range prepared by scrape foaming for thermal insulation","authors":"Yu He, Qili Zhou, Wen Wang, Zitan Yang, Zhi Liang, Zhangcheng Li, Honghao Cao, Chong Hou","doi":"10.1016/j.cej.2024.157766","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157766","url":null,"abstract":"Polyimide (PI) foams possess excellent mechanical properties and high-temperature resistance, which present significant utility in the aerospace, transportation, and microelectronics industries. The microstructure of PI foam, specifically the pore size and porosity, significantly influences its physical and mechanical properties. However, achieving both high porosity and small pore size simultaneously is greatly challenging for PI foams, especially via the foaming method. Here, we report PI foams with mean pore size of 98.1 μm and porosity of 92 % using a one-step scrape foaming method. The scraping thickness is found to be key to adjusting the pore size of the foam due to the interface effect in the initial stage, and maintaining optimal air pressure and low temperature allows slow bubble growth without bursting or merging, resulting in PI foams with high porosity and small pore size. The PI foam we fabricated exhibits excellent thermal insulating performance, with a low thermal conductivity of 20 mW/m∙K. The scrape foaming method provides an efficient and low-cost strategy for the preparation of PI foams with a tunable porous structure and is expected to find a variety of applications in thermal insulation and environmental protection.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"6 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671083","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 : 2024-11-19DOI: 10.1016/j.cej.2024.157825
Jiajia Ren, Lin Chen, Jinlei Du, Yongzhen Yang, Xuguang Liu, Yong Chen, Shiping Yu
Room temperature phosphorescence (RTP) materials have important applications in biosensing, bioimaging, drug delivery, and photodynamic therapy for tumor diagnosis and therapy owing to their long luminescence lifetimes, large Stokes shifts, and no need for real-time excitation. Carbon dots (CDs) are a new type of RTP materials, which have attracted wide attention because of their long RTP lifetime, tunable emission wavelength, low cytotoxicity, and other excellent properties compared with traditional RTP materials. However, most CDs only emit RTP in the solid state, which is quenched when dissolved in aqueous solutions. Therefore, recent studies on the synthesis and property modulation of RTP CD composites in aqueous solution have greatly expanded their applications in biomedicine. This review summarizes the latest research progress of aqueous RTP CD composites in tumor diagnosis and therapy, specifically including their synthesis methods, properties, and applications in tumor diagnosis and therapy. Beginning with the RTP emission mechanism of CDs in aqueous solutions, the interaction between CDs and matrix in RTP CD composites includes hydrogen bonding, covalent bonding, and inorganic salt confinement effects, and their structural influence laws on RTP emission are summarized. Secondly, the properties of RTP CD composites are summarized in terms of luminescence performance, photoinitiated generation of reactive oxygen species, and biotoxicity. Subsequently, the principles of RTP CD composites in biosensing, bioimaging, and tumor therapy are analyzed and the progress of their application in tumor diagnosis and therapy is reviews. Finally, the future challenges and opportunities of RTP CD composites in the biomedical field are presented to provide a reference for their controllable design and wide application.
室温磷光（RTP）材料具有发光寿命长、斯托克斯位移大、无需实时激发等特点，在生物传感、生物成像、药物传输以及肿瘤诊断和治疗的光动力疗法等领域有着重要的应用。碳点（CD）是一种新型的 RTP 材料，与传统的 RTP 材料相比，具有 RTP 寿命长、发射波长可调、细胞毒性低等优良特性，因此受到广泛关注。然而，大多数 CD 只能在固态下发射 RTP，当溶解在水溶液中时，RTP 会被淬灭。因此，近年来关于水溶液中 RTP CD 复合材料的合成和性能调控的研究大大拓展了其在生物医学领域的应用。本综述总结了水溶液 RTP CD 复合材料在肿瘤诊断和治疗中的最新研究进展，具体包括其合成方法、性质以及在肿瘤诊断和治疗中的应用。从水溶液中 CD 的 RTP 发射机理入手，总结了 RTP CD 复合材料中 CD 与基体的相互作用包括氢键、共价键和无机盐禁锢效应，以及它们对 RTP 发射的结构影响规律。其次，从发光性能、光引发活性氧生成和生物毒性等方面总结了 RTP CD 复合材料的特性。随后，分析了 RTP CD 复合材料在生物传感、生物成像和肿瘤治疗中的原理，并回顾了其在肿瘤诊断和治疗中的应用进展。最后，介绍了 RTP CD 复合材料在生物医学领域未来面临的挑战和机遇，为其可控设计和广泛应用提供参考。
{"title":"Room temperature phosphorescent carbon dot composites in aqueous solutions: synthesis, properties, and tumor diagnosis and therapy","authors":"Jiajia Ren, Lin Chen, Jinlei Du, Yongzhen Yang, Xuguang Liu, Yong Chen, Shiping Yu","doi":"10.1016/j.cej.2024.157825","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157825","url":null,"abstract":"Room temperature phosphorescence (RTP) materials have important applications in biosensing, bioimaging, drug delivery, and photodynamic therapy for tumor diagnosis and therapy owing to their long luminescence lifetimes, large Stokes shifts, and no need for real-time excitation. Carbon dots (CDs) are a new type of RTP materials, which have attracted wide attention because of their long RTP lifetime, tunable emission wavelength, low cytotoxicity, and other excellent properties compared with traditional RTP materials. However, most CDs only emit RTP in the solid state, which is quenched when dissolved in aqueous solutions. Therefore, recent studies on the synthesis and property modulation of RTP CD composites in aqueous solution have greatly expanded their applications in biomedicine. This review summarizes the latest research progress of aqueous RTP CD composites in tumor diagnosis and therapy, specifically including their synthesis methods, properties, and applications in tumor diagnosis and therapy. Beginning with the RTP emission mechanism of CDs in aqueous solutions, the interaction between CDs and matrix in RTP CD composites includes hydrogen bonding, covalent bonding, and inorganic salt confinement effects, and their structural influence laws on RTP emission are summarized. Secondly, the properties of RTP CD composites are summarized in terms of luminescence performance, photoinitiated generation of reactive oxygen species, and biotoxicity. Subsequently, the principles of RTP CD composites in biosensing, bioimaging, and tumor therapy are analyzed and the progress of their application in tumor diagnosis and therapy is reviews. Finally, the future challenges and opportunities of RTP CD composites in the biomedical field are presented to provide a reference for their controllable design and wide application.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"18 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673744","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 : 2024-11-19DOI: 10.1016/j.cej.2024.157788
Sujeong Kim, Jemin Lee, Hojun Moon, Jaehun Lee, Hyunsub Shin, Jun Sung Lee, Sang Woo Joo, Jeeyoung Yoo, Misook Kang
In this study, we introduce an innovative approach to enhance the electrochemical performance and longevity of lithium iron phosphate (LiFePO4, LFP) cathode materials through a novel saccharide-assisted unidirectional stacking method. The inherent challenges of LFP, such as low lithium-ion diffusion and limited electrical conductivity, are addressed by leveraging saccharides as binders to achieve precise alignment of LFP particles. This method facilitates the formation of unobstructed lithium-ion pathways, significantly enhancing Li+ ion diffusion rates and cycle stability. The unmodified LFP cathode exhibited a lithium-ion diffusion coefficient (DLi+) of 7.79 × 10−12 cm2 s−1, while the S5 (sucrose 5 %) LFP cathode demonstrated a superior diffusion coefficient of 3.5 × 10−10 cm2 s−1. Additionally, the S5-LFP achieved a remarkable discharge capacity of 165.1 mAh g−1 at a 0.1C rate, compared to 147.8 mAh g−1 for the unmodified LFP. The cycle stability was also significantly improved, with the S5-LFP retaining 86.3 % of its capacity after 2,000 cycles at a 5C rate, whereas the unmodified LFP retained only 79.2 % under the same conditions. These improvements are attributed to the optimized particle alignment achieved through saccharide-assisted stacking, which enhances Li+ ion diffusion and overall electrochemical performance. Additionally, the structural integrity and electrochemical stability of the S5-LFP cathodes were thoroughly validated through a comprehensive set of characterization methods and electrochemical tests, highlighting the scalability and cost-effectiveness of this technique for battery manufacturing. This breakthrough in cathode material design offers a promising pathway for the development of high-performance, durable lithium-ion batteries, particularly for applications in electric vehicles and other demanding energy storage systems.
{"title":"Optimized Li+ ion diffusion pathways in unidirectional stacked lithium iron phosphate cathodes: Enhanced electrochemical performance and long-term stability","authors":"Sujeong Kim, Jemin Lee, Hojun Moon, Jaehun Lee, Hyunsub Shin, Jun Sung Lee, Sang Woo Joo, Jeeyoung Yoo, Misook Kang","doi":"10.1016/j.cej.2024.157788","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157788","url":null,"abstract":"In this study, we introduce an innovative approach to enhance the electrochemical performance and longevity of lithium iron phosphate (LiFePO<sub>4</sub>, LFP) cathode materials through a novel saccharide-assisted unidirectional stacking method. The inherent challenges of LFP, such as low lithium-ion diffusion and limited electrical conductivity, are addressed by leveraging saccharides as binders to achieve precise alignment of LFP particles. This method facilitates the formation of unobstructed lithium-ion pathways, significantly enhancing Li<sup>+</sup> ion diffusion rates and cycle stability. The unmodified LFP cathode exhibited a lithium-ion diffusion coefficient (D<sub>Li</sub><sup>+</sup>) of 7.79 × 10<sup>−12</sup> cm<sup>2</sup> s<sup>−1</sup>, while the S5 (sucrose 5 %) LFP cathode demonstrated a superior diffusion coefficient of 3.5 × 10<sup>−10</sup> cm<sup>2</sup> s<sup>−1</sup>. Additionally, the S5-LFP achieved a remarkable discharge capacity of 165.1 mAh g<sup>−1</sup> at a 0.1C rate, compared to 147.8 mAh g<sup>−1</sup> for the unmodified LFP. The cycle stability was also significantly improved, with the S5-LFP retaining 86.3 % of its capacity after 2,000 cycles at a 5C rate, whereas the unmodified LFP retained only 79.2 % under the same conditions. These improvements are attributed to the optimized particle alignment achieved through saccharide-assisted stacking, which enhances Li<sup>+</sup> ion diffusion and overall electrochemical performance. Additionally, the structural integrity and electrochemical stability of the S5-LFP cathodes were thoroughly validated through a comprehensive set of characterization methods and electrochemical tests, highlighting the scalability and cost-effectiveness of this technique for battery manufacturing. This breakthrough in cathode material design offers a promising pathway for the development of high-performance, durable lithium-ion batteries, particularly for applications in electric vehicles and other demanding energy storage systems.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"230 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673750","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}
Simultaneous removal of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) is absolutely imperative to prevent the spread of antibiotic resistance in the environment. Herein, suitable dopants of Ti4O7 anode from the lanthanide elements were firstly selected to boost Ti4O7 electrooxidation ability according to density functional theory simulation. 3D printing technology was further adopted to prepare 3D printed lanthanide-doped reactive electrochemical membrane (REM) electrodes, which could efficiently avoid the problem of membrane clogging in the electrochemical filtration operation and increase the hydroxyl radical yield by 56–442 % compared to Ti4O7 REM. We found that complete inactivation (>8.0-log inactivation) of antibiotic resistant Escherichia coli (AR E. coli) was achieved during Nd-Ti4O7 REM (1 wt% Nd) treatment in a single pass at 4 mA cm−2, indicating significant improvement of disinfection efficiency than Ti4O7 REM (3.3-log inactivation) operated in same conditions occurred. Morphology characterization results of treated AR E. coli revealed that cytoplasmic leakage in cell membrane perforation was the main inactivation mechanism. In addition, Nd-Ti4O7 REM also exhibited better electrooxidation efficiency for ARGs removal, thereby eliminating the spread risk of antibiotic resistance. These findings greatly promoted the preparation and application of Ti4O7 REM with highly efficient electrooxidation ability in the treatment of wastewater containing an abundance of antibiotic resistant bacteria.
同时去除抗生素耐药菌（ARB）和抗生素耐药基因（ARGs）是防止环境中抗生素耐药性扩散的当务之急。在此，首先根据密度泛函理论模拟，从镧系元素中选择合适的掺杂剂来提高Ti4O7阳极的电氧化能力。进一步采用三维打印技术制备了掺杂镧系元素的三维打印反应电化学膜（REM）电极，有效避免了电化学过滤操作中膜堵塞的问题，与Ti4O7 REM相比，羟基自由基产率提高了56%-442%。我们发现，在 4 mA cm-2 的条件下一次通过 Nd-Ti4O7 REM（1 wt% Nd）处理抗生素耐药大肠杆菌（AR 大肠杆菌）时，可实现完全灭活（8.0-log 灭活），表明消毒效率比相同条件下运行的 Ti4O7 REM（3.3-log 灭活）有显著提高。经处理的 AR 大肠杆菌的形态学表征结果显示，细胞膜穿孔中的细胞质渗漏是主要的灭活机制。此外，Nd-Ti4O7 REM 在去除 ARGs 方面也表现出更高的电氧化效率，从而消除了抗生素耐药性扩散的风险。这些发现极大地推动了具有高效电氧化能力的 Ti4O7 REM 的制备和在处理含有大量抗生素耐药菌的废水中的应用。
{"title":"3D printed lanthanide-doped Ti4O7 reactive membrane for efficient electrochemical disinfection and degradation of antibiotic resistance genes","authors":"Kehao Zhang, Yuran Han, Peiheng Wang, Zhaoshuang Bu, Beibei Wang, Huanhuan Shi, Hailong Wang, Wei Zhang, Shixiang Gao, Qingguo Huang","doi":"10.1016/j.cej.2024.157829","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157829","url":null,"abstract":"Simultaneous removal of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) is absolutely imperative to prevent the spread of antibiotic resistance in the environment. Herein, suitable dopants of Ti<sub>4</sub>O<sub>7</sub> anode from the lanthanide elements were firstly selected to boost Ti<sub>4</sub>O<sub>7</sub> electrooxidation ability according to density functional theory simulation. 3D printing technology was further adopted to prepare 3D printed lanthanide-doped reactive electrochemical membrane (REM) electrodes, which could efficiently avoid the problem of membrane clogging in the electrochemical filtration operation and increase the hydroxyl radical yield by 56–442 % compared to Ti<sub>4</sub>O<sub>7</sub> REM. We found that complete inactivation (>8.0-log inactivation) of antibiotic resistant <em>Escherichia coli</em> (AR <em>E. coli</em>) was achieved during Nd-Ti<sub>4</sub>O<sub>7</sub> REM (1 wt% Nd) treatment in a single pass at 4 mA cm<sup>−2</sup>, indicating significant improvement of disinfection efficiency than Ti<sub>4</sub>O<sub>7</sub> REM (3.3-log inactivation) operated in same conditions occurred. Morphology characterization results of treated AR <em>E. coli</em> revealed that cytoplasmic leakage in cell membrane perforation was the main inactivation mechanism. In addition, Nd-Ti<sub>4</sub>O<sub>7</sub> REM also exhibited better electrooxidation efficiency for ARGs removal, thereby eliminating the spread risk of antibiotic resistance. These findings greatly promoted the preparation and application of Ti<sub>4</sub>O<sub>7</sub> REM with highly efficient electrooxidation ability in the treatment of wastewater containing an abundance of antibiotic resistant bacteria.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"14 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673777","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}
Lithium/aluminum layered double hydroxides (LDH) have been industrially applied to extract lithium from salt-lake brine. Different from traditional granulation methods, chitosan with high hydrophilicity was used as the binder of LDH in this work, and LDH/chitosan composite hydrogel granules (CLDH) with a diameter of about 1–2 mm were successfully prepared. The new granulation method is simple, cost-effective, and does not require the use of organic solvents. The chemical composition and structure of CLDH were characterized by techniques such as FTIR, XRD, FESEM, TEM, TGA, and XPS. In simulated brine with a Mg2+/Li+ ratio of 102, the maximum saturated adsorption capacity of lithium on CLDH-3 reached 12.5 mg g−1 (pH = 6.5), but it took 24 h to reach adsorption equilibrium. During the three successive cycles for the extraction of Li+ from simulated brine by the CLDH-3 column at the flow rate of 1 mL min−1, the adsorption capacities of Li+ on CLDH-3 in the three cycles were 15.4, 15.9 and 12.1 mg g−1, respectively. Moreover, deionized water (30 °C) was used as the eluent to recover lithium adsorbed on the CLDH-3 column, and the lithium recovery efficiencies reached 50.7 %, 53.6 %, and 62.8 % of the column adsorption capacities over the three cycles, respectively, and the Mg/Li ratios in the eluents were 0.47, 0.71, and 0.50, respectively. Overall, CLDH-3 exhibits good reusability, mechanical strength, structural stability, and selectivity in the process of lithium extraction from simulated salt-lake brine, and has potential industrial application value.
{"title":"Convenient synthesis of granulated Li/Al-layered double hydroxides/chitosan composite adsorbents for lithium extraction from simulated brine with a high Mg2+/Li+ ratio","authors":"Liqin Zhao, Xiaojie Zhang, Keyi Liu, Xin Liu, Yuefa Gong, Hong Peng, Wei Qi","doi":"10.1016/j.cej.2024.157780","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157780","url":null,"abstract":"Lithium/aluminum layered double hydroxides (LDH) have been industrially applied to extract lithium from salt-lake brine. Different from traditional granulation methods, chitosan with high hydrophilicity was used as the binder of LDH in this work, and LDH/chitosan composite hydrogel granules (CLDH) with a diameter of about 1–2 mm were successfully prepared. The new granulation method is simple, cost-effective, and does not require the use of organic solvents. The chemical composition and structure of CLDH were characterized by techniques such as FTIR, XRD, FESEM, TEM, TGA, and XPS. In simulated brine with a Mg<sup>2+</sup>/Li<sup>+</sup> ratio of 102, the maximum saturated adsorption capacity of lithium on CLDH-3 reached 12.5 mg g<sup>−1</sup> (pH = 6.5), but it took 24 h to reach adsorption equilibrium. During the three successive cycles for the extraction of Li<sup>+</sup> from simulated brine by the CLDH-3 column at the flow rate of 1 mL min<sup>−1</sup>, the adsorption capacities of Li<sup>+</sup> on CLDH-3 in the three cycles were 15.4, 15.9 and 12.1 mg g<sup>−1</sup>, respectively. Moreover, deionized water (30 °C) was used as the eluent to recover lithium adsorbed on the CLDH-3 column, and the lithium recovery efficiencies reached 50.7 %, 53.6 %, and 62.8 % of the column adsorption capacities over the three cycles, respectively, and the Mg/Li ratios in the eluents were 0.47, 0.71, and 0.50, respectively. Overall, CLDH-3 exhibits good reusability, mechanical strength, structural stability, and selectivity in the process of lithium extraction from simulated salt-lake brine, and has potential industrial application value.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"13 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142670801","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 : 2024-11-19DOI: 10.1016/j.cej.2024.157822
Aobo Ren, Lianghao Jia, Pan Wang, Tao Xiang, Shaobing Zhou
Conductive hydrogels are widely used in electronic skin, wearable sensing devices, human–machine interfaces, and soft robots because of their high elasticity, biocompatibility, and conformability in interfacial contact. However, hydrogels lose electrical conductivity and flexibility due to water crystallization at low temperatures, which severely limits their applications in the frigid regions. In this study, we propose to design a metal–ligand ionic hydrogel (PAASP-Zr-LiCl) through the formation of a stable coordination bond between the dicarboxylic acid group monomer poly(N-acryloyl aspartic acid) (PAASP) and zirconium ion (Zr4+). Zr4+–COO- metal-coordination complex as physical cross-linking points of the network can effectively improve the mechanical properties of hydrogels. By introducing lithium chloride (LiCl), the hydrogel obtained excellent anti-freezing properties (crystallization temperature < -80 °C) and high ionic conductivity (8.45 S/m). The LiCl molecules enhance the interaction between the polymer network and water molecules. The ionic hydrogel-based strain sensors exhibited a high gauge factor of 3.21. Combining hydrogel sensors with soft grippers can realize continuous and stable monitoring of grasping objects at low temperature of −30 °C. By integration of excellent flexibility (elongation at break 837.4 %), good ionic conductivity, high sensitivity, and excellent anti-freezing properties, the anti-freezing ionic hydrogel has a wide range of applications in the frigid regions of the plateau.
{"title":"Toughening of anti-freezing ionic hydrogels with Zr4+-dicarboxylic acid coordination complex for low temperature sensing applications","authors":"Aobo Ren, Lianghao Jia, Pan Wang, Tao Xiang, Shaobing Zhou","doi":"10.1016/j.cej.2024.157822","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157822","url":null,"abstract":"Conductive hydrogels are widely used in electronic skin, wearable sensing devices, human–machine interfaces, and soft robots because of their high elasticity, biocompatibility, and conformability in interfacial contact. However, hydrogels lose electrical conductivity and flexibility due to water crystallization at low temperatures, which severely limits their applications in the frigid regions. In this study, we propose to design a metal–ligand ionic hydrogel (PAASP-Zr-LiCl) through the formation of a stable coordination bond between the dicarboxylic acid group monomer poly(N-acryloyl aspartic acid) (PAASP) and zirconium ion (Zr<sup>4+</sup>). Zr<sup>4+</sup>–COO<sup>-</sup> metal-coordination complex as physical cross-linking points of the network can effectively improve the mechanical properties of hydrogels. By introducing lithium chloride (LiCl), the hydrogel obtained excellent anti-freezing properties (crystallization temperature < -80 °C) and high ionic conductivity (8.45 S/m). The LiCl molecules enhance the interaction between the polymer network and water molecules. The ionic hydrogel-based strain sensors exhibited a high gauge factor of 3.21. Combining hydrogel sensors with soft grippers can realize continuous and stable monitoring of grasping objects at low temperature of −30 °C. By integration of excellent flexibility (elongation at break 837.4 %), good ionic conductivity, high sensitivity, and excellent anti-freezing properties, the anti-freezing ionic hydrogel has a wide range of applications in the frigid regions of the plateau.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"57 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673748","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 : 2024-11-18DOI: 10.1016/j.cej.2024.157755
Zhicui Song, Chaohui Wei, Jicheng Jiang, Donghuang Wang, Xin Wang, Qijiu Deng, Qiang Zhao, Aijun Zhou, Hong Li, Jingze Li
The graphite-based hybrid Li-ion/metal anode holds great promise to be one of the ultimate anode choices, owing to its high specific capacity (often up to 500 mAh/g), obviously superior to 372 mAh/g of the commercial graphite anode. Unfortunately, Li deposition on the top surface of the conductive graphite host can easily drive Li dendrite growth, dead Li accumulation, and the blockage of Li+ transport pathways, leading to low host space utilization and cycling stability deterioration. Herein, a graphite host with lithiophilicity and reactive activity dual-gradient is constructed by integrating a surface insulation passivation and a bottom lithiophilicity modification to realize the “bottom-up” deposition behavior for hybrid Li-ion/metal anode. The conformal coating layer of electrical insulating and lithiophobic polymer can efficiently retard Li+ reduction and deposition on the top surface of the conductive host, while the decorated Ag nanoparticles with high lithiophilicity on the host bottom enable much lower Li nucleation barrier, thereby guiding the preferential bottom-up Li deposition. Li dendrite growth is effectively inhibited and the synergistic effects realize high space utilization of the host. Consequently, the hybrid graphite-Li anodes with 600 mAh/g of lithiation capacity (∼3.0 mAh cm−2) deliver significantly improved cycling stability over 500 cycles with a negligible capacity fading rate of 0.05 % per cycle at 1 C in LiFePO4-based full-cells (N/P ratio = 1.9).
{"title":"Double-gradient host enabling bottom-up Li deposition towards hybrid lithium-ion/metal anode with long lifespan","authors":"Zhicui Song, Chaohui Wei, Jicheng Jiang, Donghuang Wang, Xin Wang, Qijiu Deng, Qiang Zhao, Aijun Zhou, Hong Li, Jingze Li","doi":"10.1016/j.cej.2024.157755","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157755","url":null,"abstract":"The graphite-based hybrid Li-ion/metal anode holds great promise to be one of the ultimate anode choices, owing to its high specific capacity (often up to 500 mAh/g), obviously superior to 372 mAh/g of the commercial graphite anode. Unfortunately, Li deposition on the top surface of the conductive graphite host can easily drive Li dendrite growth, dead Li accumulation, and the blockage of Li<sup>+</sup> transport pathways, leading to low host space utilization and cycling stability deterioration. Herein, a graphite host with lithiophilicity and reactive activity dual-gradient is constructed by integrating a surface insulation passivation and a bottom lithiophilicity modification to realize the “bottom-up” deposition behavior for hybrid Li-ion/metal anode. The conformal coating layer of electrical insulating and lithiophobic polymer can efficiently retard Li<sup>+</sup> reduction and deposition on the top surface of the conductive host, while the decorated Ag nanoparticles with high lithiophilicity on the host bottom enable much lower Li nucleation barrier, thereby guiding the preferential bottom-up Li deposition. Li dendrite growth is effectively inhibited and the synergistic effects realize high space utilization of the host. Consequently, the hybrid graphite-Li anodes with 600 mAh/g of lithiation capacity (∼3.0 mAh cm<sup>−2</sup>) deliver significantly improved cycling stability over 500 cycles with a negligible capacity fading rate of 0.05 % per cycle at 1 C in LiFePO<sub>4</sub>-based full-cells (N/P ratio = 1.9).","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"50 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665479","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}
Aqueous zinc-ion batteries (AZIBs) are favored by researchers because of their high safety performance and abundant zinc resources. In this work, low-cost was selected as the electrolyte additive to continuously improve the problems faced by the anode. Molybdenum-based solution can be reduced on the surface of zinc anode to form a uniform protective layer, and polyoxometalate can disperse metal elements more evenly, so that Zn2+ deposition is more uniform and AZIBs has more stable cycling performance. The symmetric battery assembled after adding Polyoxometalate oxate solution can maintain a stable potential of more than 1900 h at 5mA cm−2 and 1mAh cm−2, which is three times the cycle time of the battery assembled with ZnSO4 as the electrolyte (600 h). In addition, Mo has a certain anti-corrosion effect, which can prevent the corrosion reaction on the surface of zinc anode. The Tafel diagram shows that the corrosion current decreased from 1.995 mA cm−2 to 1.584 mA cm−2 after the addition of polyoxometalate oxate solution. The contrast effect is more obvious in SEM images. Different from the traditional zinc anode surface optimization, the addition of polyoxometalate oxate solution can continuously form auxiliary nucleation sites on the negative electrode surface to make Zn2+ deposition more uniform. When Na doped vanadium dioxide was used as the cathode to form full battery, the specific capacity could still reach 143.73mAh g−1 after 1000 cycles at the current density of 2 A/g. In this study, adding low concentration of polyoxometalate oxate solution to the electrolyte can continuously generate a stable protective layer during the battery operation, providing a feasible scheme for continuous improvement of AZIBs zinc anode.
{"title":"Polyoxometalate oxate solution: An electrolyte additive to sustainably improve the anodes electrode of aqueous Zn ion batteries","authors":"Li-li Du, Zhuo Li, Wei-jia Song, Qing-peng Bao, Peng-fei Wang, Zhe Gong, Yu-hang Zhang, Yu-han Wu, Fa-nian Shi, Ming-dong Zhou, Kai Zhu","doi":"10.1016/j.cej.2024.157743","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157743","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) are favored by researchers because of their high safety performance and abundant zinc resources. In this work, low-cost was selected as the electrolyte additive to continuously improve the problems faced by the anode. Molybdenum-based solution can be reduced on the surface of zinc anode to form a uniform protective layer, and polyoxometalate can disperse metal elements more evenly, so that Zn<sup>2+</sup> deposition is more uniform and AZIBs has more stable cycling performance. The symmetric battery assembled after adding Polyoxometalate oxate solution can maintain a stable potential of more than 1900 h at 5mA cm<sup>−2</sup> and 1mAh cm<sup>−2</sup>, which is three times the cycle time of the battery assembled with ZnSO<sub>4</sub> as the electrolyte (600 h). In addition, Mo has a certain anti-corrosion effect, which can prevent the corrosion reaction on the surface of zinc anode. The Tafel diagram shows that the corrosion current decreased from 1.995 mA cm<sup>−2</sup> to 1.584 mA cm<sup>−2</sup> after the addition of polyoxometalate oxate solution. The contrast effect is more obvious in SEM images. Different from the traditional zinc anode surface optimization, the addition of polyoxometalate oxate solution can continuously form auxiliary nucleation sites on the negative electrode surface to make Zn<sup>2+</sup> deposition more uniform. When Na doped vanadium dioxide was used as the cathode to form full battery, the specific capacity could still reach 143.73mAh g<sup>−1</sup> after 1000 cycles at the current density of 2 A/g. In this study, adding low concentration of polyoxometalate oxate solution to the electrolyte can continuously generate a stable protective layer during the battery operation, providing a feasible scheme for continuous improvement of AZIBs zinc anode.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"225 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665480","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 : 2024-11-17DOI: 10.1016/j.cej.2024.157691
Luca Mastroianni, Ananias De Jesus Medina Ferrer, Anna Maria De Domenico, Kari Eränen, Martino Di Serio, Dmitry Murzin, Vincenzo Russo, Tapio Salmi
The impact of the 3D structural design on the catalytic performance was investigated in this work. Four catalyst architectures (squared honeycomb, Schwartz P, face centered cubic and gyroid), made of alumina, were designed and printed with the Digital Light Processing (DLP) printing technology. The obtained shaped catalysts were loaded in a tubular reactor and their activities were evaluated in continuous ethanol dehydration to diethyl ether. The kinetic experiments revealed that both the conversion per unit of the reactor volume and the specific activity were highly affected by the selected design of the catalyst geometry. An advanced 1-D heterogeneous mathematical model employing geometrical features of the catalyst structures was proposed to describe the experimental data. The model included local variations of contact perimeters and cross-section areas to describe the periodic architectures. The assumption of plug flow pattern in the catalyst channels was revealed to be inadequate in predicting the structure effects, thus axial dispersion effects were included to obtain a successful and statistically significant description of the experimental observations. The proposed approach forms a solid basis to describe chemical processes operated with 3D printed catalyst structures
{"title":"DLP 3D printing of alumina catalyst architectures: Design, kinetics and modeling of structure effects on catalyst performance","authors":"Luca Mastroianni, Ananias De Jesus Medina Ferrer, Anna Maria De Domenico, Kari Eränen, Martino Di Serio, Dmitry Murzin, Vincenzo Russo, Tapio Salmi","doi":"10.1016/j.cej.2024.157691","DOIUrl":"https://doi.org/10.1016/j.cej.2024.157691","url":null,"abstract":"The impact of the 3D structural design on the catalytic performance was investigated in this work. Four catalyst architectures (squared honeycomb, Schwartz P, face centered cubic and gyroid), made of alumina, were designed and printed with the Digital Light Processing (DLP) printing technology. The obtained shaped catalysts were loaded in a tubular reactor and their activities were evaluated in continuous ethanol dehydration to diethyl ether. The kinetic experiments revealed that both the conversion per unit of the reactor volume and the specific activity were highly affected by the selected design of the catalyst geometry. An advanced 1-D heterogeneous mathematical model employing geometrical features of the catalyst structures was proposed to describe the experimental data. The model included local variations of contact perimeters and cross-section areas to describe the periodic architectures. The assumption of plug flow pattern in the catalyst channels was revealed to be inadequate in predicting the structure effects, thus axial dispersion effects were included to obtain a successful and statistically significant description of the experimental observations. The proposed approach forms a solid basis to describe chemical processes operated with 3D printed catalyst structures","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"76 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142645914","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：