Lithium‐ion secondary batteries (LIB) with high energy density have attracted much attention for electric vehicle (EV) applications. However, LIBs have a safety problem because these batteries contain a flammable organic electrolyte. As such, all‐solid secondary batteries that are not flammable have been extensively reported recently. In this study, we have focused on polymer electrolytes, which is flexible and is expected to address the safety problem. However, the conventional polymer electrolytes have low electrial conductivity at room temperature. Various attempts have been made to solve this problem, such as the addition of inorganic fillers and ionic liquids; however, these composite polymer electrolytes have not yet reached a practical level of lithium‐ion conductivity. In this study, high electrical conductivity and lithium dendrite formation‐free PEO based composite electrolytes are developed with both a filler of Li6,4La3Zr1.4Ta0.6O12 and liquid plasticizers of tetraethylene glycol dimethyl ether and 1,2 dimethoxyethane. The proposed flexible polymer electrolyte shows a high electrical conduciviy of 6.01×10−4 S cm−1 at 25 °C.
能量密度高的锂离子二次电池(LIB)在电动汽车(EV)领域的应用备受关注。然而,锂离子二次电池存在安全问题,因为这些电池含有易燃的有机电解质。因此,不易燃的全固态二次电池最近得到了广泛报道。在本研究中,我们将重点放在聚合物电解质上,因为聚合物电解质具有灵活性,有望解决安全问题。然而,传统的聚合物电解质在室温下电导率较低。为解决这一问题,人们进行了各种尝试,如添加无机填料和离子液体;然而,这些复合聚合物电解质的锂离子电导率尚未达到实用水平。本研究开发了高导电性、无锂枝晶形成的基于 PEO 的复合电解质,其中既添加了 Li6,4La3Zr1.4Ta0.6O12 填料,又添加了四甘醇二甲醚和 1,2 二甲氧基乙烷等液体增塑剂。所提出的柔性聚合物电解质在 25 °C 时的电导率高达 6.01×10-4 S cm-1。
{"title":"Flexible High Lithium‐Ion Conducting PEO‐Based Solid Polymer Electrolyte with Liquid Plasticizers for High Performance Solid‐State Lithium Batteries","authors":"Ayaka Abe, Daisuke Mori, Zhichao Wang, Sou Taminato, Yasuo Takeda, Osamu Yamamoto, Nobuyuki Imanishi","doi":"10.1002/open.202400041","DOIUrl":"https://doi.org/10.1002/open.202400041","url":null,"abstract":"Lithium‐ion secondary batteries (LIB) with high energy density have attracted much attention for electric vehicle (EV) applications. However, LIBs have a safety problem because these batteries contain a flammable organic electrolyte. As such, all‐solid secondary batteries that are not flammable have been extensively reported recently. In this study, we have focused on polymer electrolytes, which is flexible and is expected to address the safety problem. However, the conventional polymer electrolytes have low electrial conductivity at room temperature. Various attempts have been made to solve this problem, such as the addition of inorganic fillers and ionic liquids; however, these composite polymer electrolytes have not yet reached a practical level of lithium‐ion conductivity. In this study, high electrical conductivity and lithium dendrite formation‐free PEO based composite electrolytes are developed with both a filler of Li<jats:sub>6,4</jats:sub>La<jats:sub>3</jats:sub>Zr<jats:sub>1.4</jats:sub>Ta<jats:sub>0.6</jats:sub>O<jats:sub>12</jats:sub> and liquid plasticizers of tetraethylene glycol dimethyl ether and 1,2 dimethoxyethane. The proposed flexible polymer electrolyte shows a high electrical conduciviy of 6.01×10<jats:sup>−4</jats:sup> S cm<jats:sup>−1</jats:sup> at 25 °C.","PeriodicalId":9831,"journal":{"name":"ChemistryOpen","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2024-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140592224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohammed Ali Saif Al-Shaibani, Thaleia Sakoleva, Dr. Luka A. Živković, Dr. Harry P. Austin, Dr. Mark Dörr, Dr. Liane Hilfert, Prof. Edgar Haak, Prof. Uwe T. Bornscheuer, Dr. Tanja Vidaković-Koch
The direct electrochemical reduction of nicotinamide adenine dinucleotide (NAD+) results in various products, complicating the regeneration of the crucial 1,4-NADH cofactor for enzymatic reactions. Previous research primarily focused on steady–state polarization to examine potential impacts on product selectivity. However, this study explores the influence of dynamic conditions on the selectivity of NAD+ reduction products by comparing two dynamic profiles with steady-state conditions. Our findings reveal that the main products, including 1,4-NADH, several dimers, and ADP-ribose, remained consistent across all conditions. A minor by–product, 1,6-NADH, was also identified. The product distribution varied depending on the experimental conditions (steady state vs. dynamic) and the concentration of NAD+, with higher concentrations and overpotentials promoting dimerization. The optimal yield of 1,4-NADH was achieved under steady–state conditions with low overpotential and NAD+ concentrations. While dynamic conditions enhanced the 1,4-NADH yield at shorter reaction times, they also resulted in a significant amount of unidentified products. Furthermore, this study assessed the potential of using pulsed electrochemical regeneration of 1,4-NADH with enoate reductase (XenB) for cyclohexenone reduction.
{"title":"Product Distribution of Steady–State and Pulsed Electrochemical Regeneration of 1,4-NADH and Integration with Enzymatic Reaction","authors":"Mohammed Ali Saif Al-Shaibani, Thaleia Sakoleva, Dr. Luka A. Živković, Dr. Harry P. Austin, Dr. Mark Dörr, Dr. Liane Hilfert, Prof. Edgar Haak, Prof. Uwe T. Bornscheuer, Dr. Tanja Vidaković-Koch","doi":"10.1002/open.202400064","DOIUrl":"10.1002/open.202400064","url":null,"abstract":"<p>The direct electrochemical reduction of nicotinamide adenine dinucleotide (NAD<sup>+</sup>) results in various products, complicating the regeneration of the crucial 1,4-NADH cofactor for enzymatic reactions. Previous research primarily focused on steady–state polarization to examine potential impacts on product selectivity. However, this study explores the influence of dynamic conditions on the selectivity of NAD<sup>+</sup> reduction products by comparing two dynamic profiles with steady-state conditions. Our findings reveal that the main products, including 1,4-NADH, several dimers, and ADP-ribose, remained consistent across all conditions. A minor by–product, 1,6-NADH, was also identified. The product distribution varied depending on the experimental conditions (steady state vs. dynamic) and the concentration of NAD<sup>+</sup>, with higher concentrations and overpotentials promoting dimerization. The optimal yield of 1,4-NADH was achieved under steady–state conditions with low overpotential and NAD<sup>+</sup> concentrations. While dynamic conditions enhanced the 1,4-NADH yield at shorter reaction times, they also resulted in a significant amount of unidentified products. Furthermore, this study assessed the potential of using pulsed electrochemical regeneration of 1,4-NADH with enoate reductase (XenB) for cyclohexenone reduction.</p>","PeriodicalId":9831,"journal":{"name":"ChemistryOpen","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/open.202400064","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140592130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guadalupe Castro, Julián Cruz‐Borbolla, Marcelo Galván, Alfredo Guevara‐García, Joel Ireta, Myrna H. Matus, Amilcar Meneses‐Viveros, Luis Ignacio Perea‐Ramírez, Miriam Pescador‐Rojas
The hydrodesulfurization (HDS) process is widely used in the industry to eliminate sulfur compounds from fuels. However, removing dibenzothiophene (DBT) and its derivatives is a challenge. Here, the key aspects that affect the efficiency of catalysts in the HDS of DBT were investigated using machine learning (ML) algorithms. The conversion of DBT and selectivity was estimated by applying Lasso, Ridge, and Random Forest regression techniques. For the estimation of conversion of DBT, Random Forest and Lasso offer adequate predictions. At the same time, regularized regressions have similar outcomes, which are suitable for selectivity estimations. According to the regression coefficient, the structural parameters are essential predictors for selectivity, highlighting the pore size, and slab length. These properties can connect with aspects like the availability of active sites. The insights gained through ML techniques about the HDS catalysts agree with the interpretations of previous experimental reports.
加氢脱硫(HDS)工艺在工业中被广泛用于消除燃料中的硫化合物。然而,去除二苯并噻吩(DBT)及其衍生物是一项挑战。在此,我们使用机器学习(ML)算法研究了影响催化剂在 DBT 加氢脱硫过程中效率的关键因素。应用 Lasso、Ridge 和 Random Forest 回归技术估算了 DBT 的转化率和选择性。对于 DBT 转化率的估计,随机森林和 Lasso 可以提供充分的预测。同时,正则化回归也有类似的结果,适用于选择性估计。根据回归系数,结构参数是选择性的重要预测因素,尤其是孔径和板坯长度。这些特性可以与活性位点的可用性等方面联系起来。通过 ML 技术获得的关于 HDS 催化剂的见解与之前实验报告的解释一致。
{"title":"Hydrodesulfurization of Dibenzothiophene: A Machine Learning Approach","authors":"Guadalupe Castro, Julián Cruz‐Borbolla, Marcelo Galván, Alfredo Guevara‐García, Joel Ireta, Myrna H. Matus, Amilcar Meneses‐Viveros, Luis Ignacio Perea‐Ramírez, Miriam Pescador‐Rojas","doi":"10.1002/open.202400062","DOIUrl":"https://doi.org/10.1002/open.202400062","url":null,"abstract":"The hydrodesulfurization (HDS) process is widely used in the industry to eliminate sulfur compounds from fuels. However, removing dibenzothiophene (DBT) and its derivatives is a challenge. Here, the key aspects that affect the efficiency of catalysts in the HDS of DBT were investigated using machine learning (ML) algorithms. The conversion of DBT and selectivity was estimated by applying Lasso, Ridge, and Random Forest regression techniques. For the estimation of conversion of DBT, Random Forest and Lasso offer adequate predictions. At the same time, regularized regressions have similar outcomes, which are suitable for selectivity estimations. According to the regression coefficient, the structural parameters are essential predictors for selectivity, highlighting the pore size, and slab length. These properties can connect with aspects like the availability of active sites. The insights gained through ML techniques about the HDS catalysts agree with the interpretations of previous experimental reports.","PeriodicalId":9831,"journal":{"name":"ChemistryOpen","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140592127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Robin Kampes, Avinash Chettri, Dr. Maria Sittig, Guangjun Yang, Dr. Stefan Zechel, Dr. Stephan Kupfer, Dr. Martin D. Hager, Prof. Dr. Benjamin Dietzek-Ivanšić, Prof. Dr. Ulrich S. Schubert
We present a luminescent Ir(III) complex featuring a bidentate halogen bond donor site capable of strong anion binding. The tailor-made Ir(III)(L)2 moiety offers a significantly higher emission quantum yield (8.4 %) compared to previous Ir(III)-based chemo-sensors (2.5 %). The successful binding of chloride, bromide and acetate is demonstrated using emission titrations. These experiments reveal association constants of up to 1.6×105 M−1. Furthermore, a new approach to evaluate the association constant by utilizing the shift of the emission was used for the first time. The experimentally observed characteristics are supported by quantum chemical simulations.
{"title":"An Iridium Complex as Bidentate Halogen Bond-Based Anion Receptor Featuring an IncreasedOptical Response","authors":"Robin Kampes, Avinash Chettri, Dr. Maria Sittig, Guangjun Yang, Dr. Stefan Zechel, Dr. Stephan Kupfer, Dr. Martin D. Hager, Prof. Dr. Benjamin Dietzek-Ivanšić, Prof. Dr. Ulrich S. Schubert","doi":"10.1002/open.202300183","DOIUrl":"10.1002/open.202300183","url":null,"abstract":"<p>We present a luminescent Ir(III) complex featuring a bidentate halogen bond donor site capable of strong anion binding. The tailor-made Ir(III)(L)<sub>2</sub> moiety offers a significantly higher emission quantum yield (8.4 %) compared to previous Ir(III)-based chemo-sensors (2.5 %). The successful binding of chloride, bromide and acetate is demonstrated using emission titrations. These experiments reveal association constants of up to 1.6×10<sup>5</sup> M<sup>−1</sup>. Furthermore, a new approach to evaluate the association constant by utilizing the shift of the emission was used for the first time. The experimentally observed characteristics are supported by quantum chemical simulations.</p>","PeriodicalId":9831,"journal":{"name":"ChemistryOpen","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2024-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/open.202300183","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140592106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}