Pub Date : 2025-10-30DOI: 10.1016/j.cplett.2025.142494
Lei Wu, Xiang Meng, Yuanzuo Li
To investigate the impact of cyano substituent positions/effects on performance of non-fullerene acceptors (NFAs), this study proposes a multi-site/multi-cyano strategy. By introducing cyano groups at ortho, meta, and para positions of 4CN-end-capped benzo[d]thiazole, three novel A-D-A NFAs (4CN-1/2/3) were designed. DFT and TD-DFT calculations indicate that all derivatives outperform molecule 4CN in frontier molecular orbitals, absorption properties, electron transport and stability; corresponding regulatory mechanisms are elucidated. Study further reveals that ortho/meta substitution designs positively influence several key parameters. Designed molecule 4CN-3 with dual CN groups exhibits superior performance across most aspects, providing valuable insights for efficient organic solar cells.
{"title":"Modulating terminal functional group to control the electronic structure, excited states and optoelectronic characteristics of non-fullerene acceptor molecules in OSCs","authors":"Lei Wu, Xiang Meng, Yuanzuo Li","doi":"10.1016/j.cplett.2025.142494","DOIUrl":"10.1016/j.cplett.2025.142494","url":null,"abstract":"<div><div>To investigate the impact of cyano substituent positions/effects on performance of non-fullerene acceptors (NFAs), this study proposes a multi-site/multi-cyano strategy. By introducing cyano groups at ortho, meta, and para positions of 4CN-end-capped benzo[<em>d</em>]thiazole, three novel A-D-A NFAs (4CN-1/2/3) were designed. DFT and TD-DFT calculations indicate that all derivatives outperform molecule 4CN in frontier molecular orbitals, absorption properties, electron transport and stability; corresponding regulatory mechanisms are elucidated. Study further reveals that ortho/meta substitution designs positively influence several key parameters. Designed molecule 4CN-3 with dual CN groups exhibits superior performance across most aspects, providing valuable insights for efficient organic solar cells.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"881 ","pages":"Article 142494"},"PeriodicalIF":3.1,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463324","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-30DOI: 10.1016/j.cplett.2025.142505
Fan Li, Xiumin Yang, Zaolong Zhang, He Xiao, Junlian Wang
To address the third-phase formation and high-acidity stripping corrosion of the traditional TBP-FeCl₃ system for Li extraction from high Mg/Li ratio salt-lake brines, this study developed a TBP-MNPK-kerosene-FeCl₃ system using 2-heptanone (MNPK) as a modifier. MNPK eliminated third-phase formation and enabled complete phase separation within 50s. Under optimal conditions (20 vol% kerosene, 40 vol% TBP), Li extraction efficiency reached 85.4 % with a Li/Mg separation factor of 315. After water scrubbing and 3 mol/L HCl stripping, the stripping solution had 5.46 g/L Li (3.12-fold enrichment) and Li/Mg ratio of 11.38. This system provides an efficient, industrial-feasible Li extraction solution.
{"title":"TBP-MNPK combinations: a promising approach for selective Lithium extraction from high Mg/Li ratio liquids","authors":"Fan Li, Xiumin Yang, Zaolong Zhang, He Xiao, Junlian Wang","doi":"10.1016/j.cplett.2025.142505","DOIUrl":"10.1016/j.cplett.2025.142505","url":null,"abstract":"<div><div>To address the third-phase formation and high-acidity stripping corrosion of the traditional TBP-FeCl₃ system for Li extraction from high Mg/Li ratio salt-lake brines, this study developed a TBP-MNPK-kerosene-FeCl₃ system using 2-heptanone (MNPK) as a modifier. MNPK eliminated third-phase formation and enabled complete phase separation within 50s. Under optimal conditions (20 <em>vol</em>% kerosene, 40 <em>vol</em>% TBP), Li extraction efficiency reached 85.4 % with a Li/Mg separation factor of 315. After water scrubbing and 3 mol/L HCl stripping, the stripping solution had 5.46 g/L Li (3.12-fold enrichment) and Li/Mg ratio of 11.38. This system provides an efficient, industrial-feasible Li extraction solution.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142505"},"PeriodicalIF":3.1,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145442443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-30DOI: 10.1016/j.cplett.2025.142503
Seung Yeon Choi , Rehana Shahin , Woo Hyeok Kim , In-Hui Hwang , Seung Jun Lee , Myong Yong Choi , Rajesh K. Yadav , Tae Wu Kim
Organic polymeric materials, composed of organic chromophores with strong light absorption, have been widely employed as heterogeneous photocatalysts in the artificial photosynthetic manner. In this study, we report covalent organic polymeric photocatalysts (COPs), which can guide directional photoinduced charge transfers operated in natural photosynthetic system. The newly-developed COPs were applied to the photocatalytic processes for the regeneration of nicotinamide adenine dinucleotide. From the combined investigations using time-resolved spectroscopies and DFT calculations, we revealed that the long-lived charge separation state in the COPs plays a crucial role in the photoinduced electron transport during the photocatalytic reaction.
{"title":"Long-lived excited state in covalent organic polymers revealed by time-resolved spectroscopy: Implications for photocatalytic applications","authors":"Seung Yeon Choi , Rehana Shahin , Woo Hyeok Kim , In-Hui Hwang , Seung Jun Lee , Myong Yong Choi , Rajesh K. Yadav , Tae Wu Kim","doi":"10.1016/j.cplett.2025.142503","DOIUrl":"10.1016/j.cplett.2025.142503","url":null,"abstract":"<div><div>Organic polymeric materials, composed of organic chromophores with strong light absorption, have been widely employed as heterogeneous photocatalysts in the artificial photosynthetic manner. In this study, we report covalent organic polymeric photocatalysts (COPs), which can guide directional photoinduced charge transfers operated in natural photosynthetic system. The newly-developed COPs were applied to the photocatalytic processes for the regeneration of nicotinamide adenine dinucleotide. From the combined investigations using time-resolved spectroscopies and DFT calculations, we revealed that the long-lived charge separation state in the COPs plays a crucial role in the photoinduced electron transport during the photocatalytic reaction.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"881 ","pages":"Article 142503"},"PeriodicalIF":3.1,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145462878","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-30DOI: 10.1016/j.cplett.2025.142507
Ping Xin , Hongjiang Li , Ziwei Huang , Kexin Su , Ying-Ying Gu
To address the challenges of low selectivity and poor stability in hydrogen peroxide (H2O2) electrosynthesis within neutral media, this study developed an O/N co-doped carbon nanotube-polytetrafluoroethylene composite cathode (designated as GF/ONCNTs-6/PTFE). Through precise control of the synergistic effects between pyrrolic-N doping (40.7 %) and carboxyl/ether functional groups, the adsorption of *OOH intermediates was significantly enhanced; simultaneously, PTFE micro-cracks were employed to establish triple-phase interfaces for facilitated oxygen diffusion. The cathode achieved a high H₂O₂ yield of 139.45 mg/L under neutral conditions (pH 7), with a current efficiency of 67.06 %, and exhibited only 8.2 % activity loss after 10 cycles. In an integrated electro-Fenton system, it accomplished 98.8 % degradation of methyl orange within 2 h under optimal conditions. This work demonstrates that defect engineering and O/N functionalization in composite cathodes significantly boost 2e− ORR efficiency, offering a promising laboratory-scale platform for electrochemical wastewater purification
{"title":"O/N co-doped CNT-PTFE composite cathode for neutral H₂O₂ electrosynthesis and stable electro-Fenton degradation of dye","authors":"Ping Xin , Hongjiang Li , Ziwei Huang , Kexin Su , Ying-Ying Gu","doi":"10.1016/j.cplett.2025.142507","DOIUrl":"10.1016/j.cplett.2025.142507","url":null,"abstract":"<div><div>To address the challenges of low selectivity and poor stability in hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) electrosynthesis within neutral media, this study developed an O/N <em>co</em>-doped carbon nanotube-polytetrafluoroethylene composite cathode (designated as GF/ONCNTs-6/PTFE). Through precise control of the synergistic effects between pyrrolic-N doping (40.7 %) and carboxyl/ether functional groups, the adsorption of *OOH intermediates was significantly enhanced; simultaneously, PTFE micro-cracks were employed to establish triple-phase interfaces for facilitated oxygen diffusion. The cathode achieved a high H₂O₂ yield of 139.45 mg/L under neutral conditions (pH 7), with a current efficiency of 67.06 %, and exhibited only 8.2 % activity loss after 10 cycles. In an integrated electro-Fenton system, it accomplished 98.8 % degradation of methyl orange within 2 h under optimal conditions. This work demonstrates that defect engineering and O/N functionalization in composite cathodes significantly boost 2e<sup>−</sup> ORR efficiency, offering a promising laboratory-scale platform for electrochemical wastewater purification</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"881 ","pages":"Article 142507"},"PeriodicalIF":3.1,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145462881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-29DOI: 10.1016/j.cplett.2025.142504
Xiaolin Zhu , Xingzhu Tang , Ye Wang , Chaofan Sun
The detection mechanism of fluorescent probe 2-(5-bromo-2-((tert-butyldiphenylsilyl)oxy)phenyl)imidazo[1,2-a]pyridine (HIPS-Br) for F− ions and the detailed excited state intramolecular proton transfer (ESIPT) process of its product 4-bromo-2-(imidazo[1,2-a]pyridin-2-yl) phenol (HIP–Br) are revealed by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). To further demonstrate the proton transfer process, we constructed the potential energy curves (PECs) of HIP-Br in ground and excited states and concluded that the proton transfer process is apt to occur in the S1 state. In addition, the energy gap and absorption and fluorescence spectra are applied to evaluate the process of detecting fluoride ion (F−).
{"title":"A fluorescent probe 2-(5-bromo-2-((tert-butyldiphenylsilyl)oxy)phenyl)imidazo[1,2-a]pyridine for the detection of F−: Theoretical investigation on the ESIPT mechanism","authors":"Xiaolin Zhu , Xingzhu Tang , Ye Wang , Chaofan Sun","doi":"10.1016/j.cplett.2025.142504","DOIUrl":"10.1016/j.cplett.2025.142504","url":null,"abstract":"<div><div>The detection mechanism of fluorescent probe 2-(5-bromo-2-((<em>tert</em>-butyldiphenylsilyl)oxy)phenyl)imidazo[1,2-<em>a</em>]pyridine (HIPS-Br) for F<sup>−</sup> ions and the detailed excited state intramolecular proton transfer (ESIPT) process of its product 4-bromo-2-(imidazo[1,2-<em>a</em>]pyridin-2-yl) phenol (HIP–Br) are revealed by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). To further demonstrate the proton transfer process, we constructed the potential energy curves (PECs) of HIP-Br in ground and excited states and concluded that the proton transfer process is apt to occur in the S<sub>1</sub> state. In addition, the energy gap and absorption and fluorescence spectra are applied to evaluate the process of detecting fluoride ion (F<sup>−</sup>).</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"881 ","pages":"Article 142504"},"PeriodicalIF":3.1,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-29DOI: 10.1016/j.cplett.2025.142500
Xiaoxiao Guan , Guojun Zhu , Juexian Cao
The intricate coupling between crystallographic defects and magnetic order in ferromagnetic semiconductors poses a significant challenge for spintronics. We introduce a conceptual framework showing that defect formation energy includes a magnetic contribution directly proportional to the change in local spin-exchange interactions. Our first-principles calculations on monolayer CrI3 corroborate this model, revealing that growing materials above their Curie temperature can suppress defect formation. This work provides fundamental insight into defect physics and offers a practical strategy for synthesizing high-quality materials for spintronic devices.
{"title":"Interplay of magnetic order and defect thermodynamics: A first-principles study of CrI3","authors":"Xiaoxiao Guan , Guojun Zhu , Juexian Cao","doi":"10.1016/j.cplett.2025.142500","DOIUrl":"10.1016/j.cplett.2025.142500","url":null,"abstract":"<div><div>The intricate coupling between crystallographic defects and magnetic order in ferromagnetic semiconductors poses a significant challenge for spintronics. We introduce a conceptual framework showing that defect formation energy includes a magnetic contribution directly proportional to the change in local spin-exchange interactions. Our first-principles calculations on monolayer CrI<sub>3</sub> corroborate this model, revealing that growing materials above their Curie temperature can suppress defect formation. This work provides fundamental insight into defect physics and offers a practical strategy for synthesizing high-quality materials for spintronic devices.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"881 ","pages":"Article 142500"},"PeriodicalIF":3.1,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413126","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Brønsted acid–base properties of ethaline, composed of choline chloride and ethylene glycol, were investigated as a representative deep eutectic solvent (DES). Rigorous potentiometric titrations with a hydrogen electrode were performed for the first time in DES to determine the autoprotolysis constant and the pKa values of some weak acids. These results revealed a ∼ 4 unit shift in pH relative to water and established the pH window of the DES, which allows direct conversion of the pH value between the DES and conventional solvents. IS-FET and glass electrodes were also evaluated, confirming practical applicability.
{"title":"The “pH-window” of a representative deep eutectic solvent and evaluation of electrodes for pH measurement","authors":"Ryo Kanzaki, Tomoya Hidaka, Shinji Tajima, Hitoshi Kodamatani, Takashi Tomiyasu","doi":"10.1016/j.cplett.2025.142475","DOIUrl":"10.1016/j.cplett.2025.142475","url":null,"abstract":"<div><div>The Brønsted acid–base properties of ethaline, composed of choline chloride and ethylene glycol, were investigated as a representative deep eutectic solvent (DES). Rigorous potentiometric titrations with a hydrogen electrode were performed for the first time in DES to determine the autoprotolysis constant and the p<em>K</em><sub>a</sub> values of some weak acids. These results revealed a ∼ 4 unit shift in pH relative to water and established the pH window of the DES, which allows direct conversion of the pH value between the DES and conventional solvents. IS-FET and glass electrodes were also evaluated, confirming practical applicability.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"881 ","pages":"Article 142475"},"PeriodicalIF":3.1,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145462879","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In complex marine environments, the search for efficient antibacterial materials has become a research hotspot to combat marine biofouling. BiOI@BiVO4 heterojunctions were fabricated by the hydrothermal processes for use in antibacterial field. BiOI@BiVO4 heterojunction shows superior antibacterial performance to BiVO4, with >99.99 % Pseudomonas sp. killed in 4 h. Further photoelectrochemical experiments have shown the unique band structure greatly promotes the separation efficiency of photoinduced charge carriers and lowers the recombination rate of e−-h+, and thereby generates more highly oxidizing free radicals, achieving efficient sterilization. This research furnishes promising concepts and orientations for the evolution of high-efficiency antibacterial materials.
{"title":"Synergistic effect of Fermi level regulation and oxygen defect engineering on enhancing photocatalytic degradation performance of BiVO4/BiOI","authors":"Tianyuan Xiao , Yong Li , Xiaoya Ding , Guangming Yin","doi":"10.1016/j.cplett.2025.142502","DOIUrl":"10.1016/j.cplett.2025.142502","url":null,"abstract":"<div><div>In complex marine environments, the search for efficient antibacterial materials has become a research hotspot to combat marine biofouling. BiOI@BiVO<sub>4</sub> heterojunctions were fabricated by the hydrothermal processes for use in antibacterial field. BiOI@BiVO<sub>4</sub> heterojunction shows superior antibacterial performance to BiVO<sub>4</sub>, with >99.99 % <em>Pseudomonas</em> sp. killed in 4 h. Further photoelectrochemical experiments have shown the unique band structure greatly promotes the separation efficiency of photoinduced charge carriers and lowers the recombination rate of e<sup>−</sup>-h<sup>+</sup>, and thereby generates more highly oxidizing free radicals, achieving efficient sterilization. This research furnishes promising concepts and orientations for the evolution of high-efficiency antibacterial materials.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"882 ","pages":"Article 142502"},"PeriodicalIF":3.1,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-27DOI: 10.1016/j.cplett.2025.142501
Chao Li , Chunyu Wang , Jiaqin Huang , Jizhang Chen , Qinghua Tian , Wei Zhang
Herein, a high-performance Si-based anode (Si@SnO2@C) has been obtained by semi-embedded integration of ultrafine SnO2 nanoparticles onto the surface of cost-effective irregular Si particles and further coated with an ultrathin carbon through a simple route. The results verify that the in-situ conversion of SnO2 into LixSn during lithiation process contributes to superb lithium storage performance of the Si particles, such as high capacity (1071.2 mAh g−1 after 500 cycles at 400 mA g−1) and long lifespan (1000 cycles). Finally, this study might be able to offer a viable strategy for facilely preparing Si-based anodes with advanced performance for lithium-ion batteries.
本文通过将超细SnO2纳米颗粒半嵌入集成到经济高效的不规则Si颗粒表面，并通过简单的方法在表面涂覆超薄碳，获得了高性能的Si基阳极（Si@SnO2@C）。结果表明，在锂化过程中将SnO2原位转化为LixSn有助于Si颗粒具有优异的锂存储性能，如高容量（在400 mA g−1下循环500次后达到1071.2 mAh g−1）和长寿命（1000次循环）。最后，这项研究可能能够提供一种可行的策略，以方便地制备具有先进性能的锂离子电池硅基阳极。
{"title":"Durable lithium storage of Si anode enabled by semi-embedded integration of SnO2 onto surface","authors":"Chao Li , Chunyu Wang , Jiaqin Huang , Jizhang Chen , Qinghua Tian , Wei Zhang","doi":"10.1016/j.cplett.2025.142501","DOIUrl":"10.1016/j.cplett.2025.142501","url":null,"abstract":"<div><div>Herein, a high-performance Si-based anode (Si@SnO<sub>2</sub>@C) has been obtained by semi-embedded integration of ultrafine SnO<sub>2</sub> nanoparticles onto the surface of cost-effective irregular Si particles and further coated with an ultrathin carbon through a simple route. The results verify that the <em>in-situ</em> conversion of SnO<sub>2</sub> into Li<sub><em>x</em></sub>Sn during lithiation process contributes to superb lithium storage performance of the Si particles, such as high capacity (1071.2 mAh g<sup>−1</sup> after 500 cycles at 400 mA g<sup>−1</sup>) and long lifespan (1000 cycles). Finally, this study might be able to offer a viable strategy for facilely preparing Si-based anodes with advanced performance for lithium-ion batteries.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"881 ","pages":"Article 142501"},"PeriodicalIF":3.1,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-25DOI: 10.1016/j.cplett.2025.142499
Ciming Wang , Pengrui Zhang , Lianjing Mao , Chunsen Ye , Tianyu Zheng , Xiao Li , Wei Sun , Jinhe Sun
This study systematically investigates the competitive effects of H+, NH₄+, and OH− on Li+ migration and isotope separation during electromigration. Combined experimental and DFT analyses reveal that H+ and NH₄+ significantly inhibit both Li+ transport and isotopic partitioning, primarily through competitive chelation with 4-aminobenzo-15-crown-5, with H+ exhibiting the strongest interference. DFT results confirm the binding affinity order: H+ > NH₄+ > Li+. Additionally, OH− accumulation further impedes Li+ migration and system stability. These findings highlight the critical importance of controlling electrolyte pH and minimizing competing ion concentrations, providing essential guidance for optimizing high-efficiency lithium isotope separation systems.
{"title":"Electromigration separation of lithium isotopes: the competitive effect of ions","authors":"Ciming Wang , Pengrui Zhang , Lianjing Mao , Chunsen Ye , Tianyu Zheng , Xiao Li , Wei Sun , Jinhe Sun","doi":"10.1016/j.cplett.2025.142499","DOIUrl":"10.1016/j.cplett.2025.142499","url":null,"abstract":"<div><div>This study systematically investigates the competitive effects of H<sup>+</sup>, NH₄<sup>+</sup>, and OH<sup>−</sup> on Li<sup>+</sup> migration and isotope separation during electromigration. Combined experimental and DFT analyses reveal that H<sup>+</sup> and NH₄<sup>+</sup> significantly inhibit both Li<sup>+</sup> transport and isotopic partitioning, primarily through competitive chelation with 4-aminobenzo-15-crown-5, with H<sup>+</sup> exhibiting the strongest interference. DFT results confirm the binding affinity order: H<sup>+</sup> > NH₄<sup>+</sup> > Li<sup>+</sup>. Additionally, OH<sup>−</sup> accumulation further impedes Li<sup>+</sup> migration and system stability. These findings highlight the critical importance of controlling electrolyte pH and minimizing competing ion concentrations, providing essential guidance for optimizing high-efficiency lithium isotope separation systems.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"882 ","pages":"Article 142499"},"PeriodicalIF":3.1,"publicationDate":"2025-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413184","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号