Chun-Xiu Liu, Yao Yao, Zi-Wen Zhou, Song Qin, Zhi-Peng Yu, Fei-Yan Tao, Wen-Dian Li, Xiao-Qi Yu, Na Wang
The strategy of photocatalyzed E→Z isomerization of olefins to access thermodynamically less stable Z-alkenes has recently received considerable attention. Here, we have discovered a sensitizer of hydroxyaromatic aldehyde that can rapidly achieve olefin E→Z isomerization under blue light irradiation. Notably, 2-hydroxybenzene-1,3,5-tricarbaldehyde, when assisted by blue light, can achieve efficient and selective conversion within just 5 minutes (Z/E=92 : 8). The reaction can be successfully scaled up to gram scale, and exhibits remarkable reactivity toward various derivatives of ethyl cinnamate (27 examples) and other olefins. Furthermore, the former can be directly cyclized by a hydroxyl derivative to produce 4-substituted coumarin. The prominent preponderance of this method includes being metal-free, efficient, convenient, no by-products and achieving high selectivity. Correlation of sensitizer triplet energy (ET) and preliminary mechanistic experiments indicate that the accomplishment of this reaction is based on the selective excitation mechanism.
{"title":"Application of Hydroxyaromatic Aldehydes in Ultra-Efficient and Metal-Free Photocatalytic E→Z Isomerization of Olefin.","authors":"Chun-Xiu Liu, Yao Yao, Zi-Wen Zhou, Song Qin, Zhi-Peng Yu, Fei-Yan Tao, Wen-Dian Li, Xiao-Qi Yu, Na Wang","doi":"10.1002/cssc.202401387","DOIUrl":"https://doi.org/10.1002/cssc.202401387","url":null,"abstract":"<p><p>The strategy of photocatalyzed E→Z isomerization of olefins to access thermodynamically less stable Z-alkenes has recently received considerable attention. Here, we have discovered a sensitizer of hydroxyaromatic aldehyde that can rapidly achieve olefin E→Z isomerization under blue light irradiation. Notably, 2-hydroxybenzene-1,3,5-tricarbaldehyde, when assisted by blue light, can achieve efficient and selective conversion within just 5 minutes (Z/E=92 : 8). The reaction can be successfully scaled up to gram scale, and exhibits remarkable reactivity toward various derivatives of ethyl cinnamate (27 examples) and other olefins. Furthermore, the former can be directly cyclized by a hydroxyl derivative to produce 4-substituted coumarin. The prominent preponderance of this method includes being metal-free, efficient, convenient, no by-products and achieving high selectivity. Correlation of sensitizer triplet energy (E<sub>T</sub>) and preliminary mechanistic experiments indicate that the accomplishment of this reaction is based on the selective excitation mechanism.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing improved catalysts for sustainable chemical processes often involves understanding atomistic origins of catalytic activity, selectivity, and stability. Using density functional theory and steady-state kinetic analyses, we probe the elementary steps that form decomposition products that limit selectivity in vinyl acetate (VA) synthesis on Pd surfaces covered with acetate species. Acetate formation and coupling with ethylene control the VA formation catalytic cycle and steady-state coverage, but acetate and ethylene can separately decompose to form CO2. Both decompositions involve initial C-H activations at acetate vacancies, followed by additional C-H activations and eventual C-O formations and C-C cleavages involving reactions with molecular oxygen. Acetate decomposition paths with non-oxidative kinetically-relevant steps exhibit similar free energy barriers to oxidative paths. In contrast, the non-oxidative ethylene path involving an ethylidyne intermediate exhibits a much lower barrier than paths with oxidative kinetically-relevant steps. Ethylene decomposition is very facile at low coverages but is more coverage-sensitive, leading to similar decomposition and VA formation barriers at coverages accessible at steady state, which is consistent with moderate VA selectivity in measurements and ethylene vs. acetate decomposition contributions assessed from regressed kinetic parameters. These insights provide a detailed framework for describing VA synthesis rates and selectivity on metallic catalyst surfaces.
{"title":"Mechanistic Insights on Coverage-Dependent Selectivity Limitations in Vinyl Acetate Synthesis.","authors":"Gregory L Novotny, Prashant Deshlahra","doi":"10.1002/cssc.202401911","DOIUrl":"https://doi.org/10.1002/cssc.202401911","url":null,"abstract":"<p><p>Developing improved catalysts for sustainable chemical processes often involves understanding atomistic origins of catalytic activity, selectivity, and stability. Using density functional theory and steady-state kinetic analyses, we probe the elementary steps that form decomposition products that limit selectivity in vinyl acetate (VA) synthesis on Pd surfaces covered with acetate species. Acetate formation and coupling with ethylene control the VA formation catalytic cycle and steady-state coverage, but acetate and ethylene can separately decompose to form CO2. Both decompositions involve initial C-H activations at acetate vacancies, followed by additional C-H activations and eventual C-O formations and C-C cleavages involving reactions with molecular oxygen. Acetate decomposition paths with non-oxidative kinetically-relevant steps exhibit similar free energy barriers to oxidative paths. In contrast, the non-oxidative ethylene path involving an ethylidyne intermediate exhibits a much lower barrier than paths with oxidative kinetically-relevant steps. Ethylene decomposition is very facile at low coverages but is more coverage-sensitive, leading to similar decomposition and VA formation barriers at coverages accessible at steady state, which is consistent with moderate VA selectivity in measurements and ethylene vs. acetate decomposition contributions assessed from regressed kinetic parameters. These insights provide a detailed framework for describing VA synthesis rates and selectivity on metallic catalyst surfaces.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Arata Matsui, Deandra Ayu Putri, Morgan L Thomas, Yuko Takeoka, Masahiro Rikukawa, Masahiro Yoshizawa-Fujita
Cellulose is one of the main components of plant cell walls, abundant on earth, and can be acquired at a low cost. Furthermore, there has been increasing interest in its use in environmentally friendly, carbon-neutral, sustainable materials. It is expected that the applications of cellulose will expand with the development of a simple processing method. In this study, we dissolved cellulose in aqueous N-butyl-N-methylpyrrolidinium hydroxide solution ([C4mpyr][OH]/H2O) and investigated the cellulose regeneration process based on changes in solubility upon application of CO2 gas. We investigated the effect of transformation of the anion chemical structure on cellulose solubility by flowing CO2 gas into [C4mpyr][OH]/H2O and conducted pH, FT-IR, and 13C NMR measurements. We observed that the changes in anion structure allowed for the modulation of cellulose solubility in [C4mpyr][OH]/H2O, thus establishing a simple and safe cellulose regeneration process. This regeneration process was also applied to enable the production of cellulose hydrogels. The hydrogel formed using this method was revealed to have higher mechanical strength than an analogous hydrogel produced using the same dissolution solvent with the addition of a cross-linker. The ability to produce cellulose-based hydrogels of different mechanical properties is expected to expand the possible applications.
{"title":"A Simple Regeneration Process Using a CO2-Switchable-Polarity Solvent for Cellulose Hydrogels.","authors":"Arata Matsui, Deandra Ayu Putri, Morgan L Thomas, Yuko Takeoka, Masahiro Rikukawa, Masahiro Yoshizawa-Fujita","doi":"10.1002/cssc.202401848","DOIUrl":"https://doi.org/10.1002/cssc.202401848","url":null,"abstract":"<p><p>Cellulose is one of the main components of plant cell walls, abundant on earth, and can be acquired at a low cost. Furthermore, there has been increasing interest in its use in environmentally friendly, carbon-neutral, sustainable materials. It is expected that the applications of cellulose will expand with the development of a simple processing method. In this study, we dissolved cellulose in aqueous N-butyl-N-methylpyrrolidinium hydroxide solution ([C4mpyr][OH]/H2O) and investigated the cellulose regeneration process based on changes in solubility upon application of CO2 gas. We investigated the effect of transformation of the anion chemical structure on cellulose solubility by flowing CO2 gas into [C4mpyr][OH]/H2O and conducted pH, FT-IR, and 13C NMR measurements. We observed that the changes in anion structure allowed for the modulation of cellulose solubility in [C4mpyr][OH]/H2O, thus establishing a simple and safe cellulose regeneration process. This regeneration process was also applied to enable the production of cellulose hydrogels. The hydrogel formed using this method was revealed to have higher mechanical strength than an analogous hydrogel produced using the same dissolution solvent with the addition of a cross-linker. The ability to produce cellulose-based hydrogels of different mechanical properties is expected to expand the possible applications.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nan Wei, Yawen Guo, Haoming Song, Yahui Liu, Hao Lu, Zhishan Bo
With the rapid advancement of non-fullerene acceptors (NFAs), the power conversion efficiency (PCE) of organic solar cells (OSCs) has surpassed the 20% threshold, highlighting their considerable potential as next-generation energy conversion devices. In comparison to inorganic or perovskite solar cells, the open-circuit voltage (Voc) of OSCs is constrained by substantial non-radiative energy losses (ΔEnr), leading to values notably below those anticipated by the Shockley-Queisser limit. In OSCs, non-radiative energy losses are intimately associated with the electroluminescent quantum efficiency (EQEEL) of charge transfer states, which is in turn directly affected by the photoluminescence quantum yield (PLQY) of acceptor materials. Consequently, enhancing the PLQY of low-bandgap acceptor materials has emerged as a pivotal strategy to effectively mitigate ΔEnr. This review article delves into the intrinsic correlation between molecular structure and PLQY from the vantage point of acceptor material design. It further explores methodologies for designing acceptor materials exhibiting high PLQY, with the ultimate goal of realizing OSCs that combine high efficiency with minimal ΔEnr.
{"title":"Reducing Non-Radiative Energy Losses in Non-fullerene Organic Solar Cells.","authors":"Nan Wei, Yawen Guo, Haoming Song, Yahui Liu, Hao Lu, Zhishan Bo","doi":"10.1002/cssc.202402169","DOIUrl":"https://doi.org/10.1002/cssc.202402169","url":null,"abstract":"<p><p>With the rapid advancement of non-fullerene acceptors (NFAs), the power conversion efficiency (PCE) of organic solar cells (OSCs) has surpassed the 20% threshold, highlighting their considerable potential as next-generation energy conversion devices. In comparison to inorganic or perovskite solar cells, the open-circuit voltage (Voc) of OSCs is constrained by substantial non-radiative energy losses (ΔEnr), leading to values notably below those anticipated by the Shockley-Queisser limit. In OSCs, non-radiative energy losses are intimately associated with the electroluminescent quantum efficiency (EQEEL) of charge transfer states, which is in turn directly affected by the photoluminescence quantum yield (PLQY) of acceptor materials. Consequently, enhancing the PLQY of low-bandgap acceptor materials has emerged as a pivotal strategy to effectively mitigate ΔEnr. This review article delves into the intrinsic correlation between molecular structure and PLQY from the vantage point of acceptor material design. It further explores methodologies for designing acceptor materials exhibiting high PLQY, with the ultimate goal of realizing OSCs that combine high efficiency with minimal ΔEnr.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anastasia O Komarova, Cicely M Warne, Hugo Pétremand, Laura König-Mattern, Johannes Stöckelmaier, Chris Oostenbrink, Georg M Guebitz, Jeremy Luterbacher, Alessandro Pellis
The use of organic solvents in academic research and industry applications is facing increasing regulatory pressure due to environmental and health concerns. Consequently, there is a growing demand for sustainable solvents, particularly in the enzymatic synthesis and processing of polyesters. Biocatalysts offer a sustainable method for producing these materials; however, achieving high molecular weights often necessitates use of solvents. In this work, we introduce a new class of alternative aprotic solvents with medium polarity produced directly from agricultural waste biomass in up to 83 mol% yield (on xylan basis). The new solvents have a largely unmodified xylose core and acetal functionality, yet they show no peroxide formation and provide reduced flammability risk. We also demonstrate their successful application in enzymatic polycondensation reactions with Candida antarctica lipase B (CaLB). In particular, the solvent dibutylxylose (DBX) outperformed the hazardous solvent diphenyl ether and facilitated polycondensation of the lignin-derived diester pyridine-2,4-dicarboxylate, yielding polyesters with a Mn of >15 kDa. Computational modelling studies provided further insight into the molecular structure and dynamics of CaLB in the presence of new solvents. Lastly, up to 98 wt% of the new xylose acetals were successfully recovered and recycled, further contributing to the sustainability of the overall process.
{"title":"Xylose Acetals - a New Class of Sustainable Solvents and Their Application in Enzymatic Polycondensation.","authors":"Anastasia O Komarova, Cicely M Warne, Hugo Pétremand, Laura König-Mattern, Johannes Stöckelmaier, Chris Oostenbrink, Georg M Guebitz, Jeremy Luterbacher, Alessandro Pellis","doi":"10.1002/cssc.202401877","DOIUrl":"10.1002/cssc.202401877","url":null,"abstract":"<p><p>The use of organic solvents in academic research and industry applications is facing increasing regulatory pressure due to environmental and health concerns. Consequently, there is a growing demand for sustainable solvents, particularly in the enzymatic synthesis and processing of polyesters. Biocatalysts offer a sustainable method for producing these materials; however, achieving high molecular weights often necessitates use of solvents. In this work, we introduce a new class of alternative aprotic solvents with medium polarity produced directly from agricultural waste biomass in up to 83 mol% yield (on xylan basis). The new solvents have a largely unmodified xylose core and acetal functionality, yet they show no peroxide formation and provide reduced flammability risk. We also demonstrate their successful application in enzymatic polycondensation reactions with Candida antarctica lipase B (CaLB). In particular, the solvent dibutylxylose (DBX) outperformed the hazardous solvent diphenyl ether and facilitated polycondensation of the lignin-derived diester pyridine-2,4-dicarboxylate, yielding polyesters with a Mn of >15 kDa. Computational modelling studies provided further insight into the molecular structure and dynamics of CaLB in the presence of new solvents. Lastly, up to 98 wt% of the new xylose acetals were successfully recovered and recycled, further contributing to the sustainability of the overall process.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The transformation of CO2 into chemical building blocks for various industries is considered a key technology in a net-zero energy future. To realize this, plasma discharges are one of the most promising approaches thanks to their electron-driven reactions and high operational flexibility. Most studies focused on room-temperature and vibrationally-excited discharges, however, lately, the importance of thermal reactions is considered. Therefore, we developed a temperature-dependent plasma-chemical reaction mechanism to investigate the temperature dependence of plasma-based CO2 conversion. Here, we present the various effects of thermally-driven reactions on the CO2 conversion as a function of the gas temperature and specific energy input. Our analysis pinpointed the key reactions controlling the plasma-based CO2 conversion, shifting from an electron-driven to a thermal-driven regime. Additionally, we used the mechanism to verify the theoretical upper boundary of the process' energy efficiency, and discussed how our findings could lead to the further development and optimization of plasma discharges for efficient CO₂ conversion in the future.
{"title":"Temperature-Dependent Kinetics of Plasma-Based CO2 Conversion: Interplay of Electron-Driven and Thermal-Driven Chemistry.","authors":"Aswath Mohanan, Ramses Snoeckx, Min Suk Cha","doi":"10.1002/cssc.202401526","DOIUrl":"10.1002/cssc.202401526","url":null,"abstract":"<p><p>The transformation of CO2 into chemical building blocks for various industries is considered a key technology in a net-zero energy future. To realize this, plasma discharges are one of the most promising approaches thanks to their electron-driven reactions and high operational flexibility. Most studies focused on room-temperature and vibrationally-excited discharges, however, lately, the importance of thermal reactions is considered. Therefore, we developed a temperature-dependent plasma-chemical reaction mechanism to investigate the temperature dependence of plasma-based CO2 conversion. Here, we present the various effects of thermally-driven reactions on the CO2 conversion as a function of the gas temperature and specific energy input. Our analysis pinpointed the key reactions controlling the plasma-based CO2 conversion, shifting from an electron-driven to a thermal-driven regime. Additionally, we used the mechanism to verify the theoretical upper boundary of the process' energy efficiency, and discussed how our findings could lead to the further development and optimization of plasma discharges for efficient CO₂ conversion in the future.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peili Zhang, Zhiyong Fang, Yunxuan Ding, Song Yuan, Linqin Wang, Mei Wang, Fusheng Li, Xiujuan Wu, Licheng Sun
Renewable energy driven electrochemically hydrogenation of unsaturated C-N bonds with water as a hydrogen source provides an eco-friendly route for amine production. However, the potential commercial applications of this strategy were limited by the lack of relevant extended research. Here we demonstrate an efficient electrochemical hydrogenation system for the formation of amines from nitriles by a vacancy-rich copper phosphide catalyst. The catalytic system achieves a yield of 99% and a Faraday efficiency of 99% for the hydrogenation of benzonitrile. Mechanism study shows that benzonitrile is spontaneously adsorbed on the electrode surface and the electrogenerated active adsorbed hydrogen is the key reactive intermediate for hydrogenation. Theoretical calculation results show that vacancy-induced active sites chemisorb the N atom, thus accelerating C≡N bond activation for hydrogenation. Encouragingly, good yields of amines (≥99%) are obtained when benzonitrile is replaced by a series of aromatic nitriles, heterocyclic nitriles, aliphatic nitriles, and imines. These results show the general applicability of this method for the synthesis of various amines.
以水为氢源的不饱和 C-N 键的可再生能源驱动电化学氢化为胺的生产提供了一条生态友好型途径。然而,由于缺乏相关的扩展研究,这一策略的潜在商业应用受到了限制。在此,我们展示了一种利用富空位磷化铜催化剂从腈形成胺的高效电化学氢化系统。在苯甲腈的氢化过程中,该催化系统的产率达到 99%,法拉第效率达到 99%。机理研究表明,苯腈自发吸附在电极表面,电生活性吸附氢是氢化的关键反应中间体。理论计算的结果表明,空位诱导的活性位点与 N 原子发生化学吸附,从而加速了 C≡N 键活化以实现氢化。令人鼓舞的是,当苯甲腈被一系列芳香族腈、杂环腈、脂肪族腈和亚胺取代时,胺的产量很高(≥99%)。这些结果表明这种方法普遍适用于合成各种胺。
{"title":"Electrocatalytic Hydrogenation and Deuteration of Unsaturated C-N Bonds to Amines with Vacancy-rich Cu3P Nanowires as Catalysts in Aqueous Solution.","authors":"Peili Zhang, Zhiyong Fang, Yunxuan Ding, Song Yuan, Linqin Wang, Mei Wang, Fusheng Li, Xiujuan Wu, Licheng Sun","doi":"10.1002/cssc.202401601","DOIUrl":"https://doi.org/10.1002/cssc.202401601","url":null,"abstract":"<p><p>Renewable energy driven electrochemically hydrogenation of unsaturated C-N bonds with water as a hydrogen source provides an eco-friendly route for amine production. However, the potential commercial applications of this strategy were limited by the lack of relevant extended research. Here we demonstrate an efficient electrochemical hydrogenation system for the formation of amines from nitriles by a vacancy-rich copper phosphide catalyst. The catalytic system achieves a yield of 99% and a Faraday efficiency of 99% for the hydrogenation of benzonitrile. Mechanism study shows that benzonitrile is spontaneously adsorbed on the electrode surface and the electrogenerated active adsorbed hydrogen is the key reactive intermediate for hydrogenation. Theoretical calculation results show that vacancy-induced active sites chemisorb the N atom, thus accelerating C≡N bond activation for hydrogenation. Encouragingly, good yields of amines (≥99%) are obtained when benzonitrile is replaced by a series of aromatic nitriles, heterocyclic nitriles, aliphatic nitriles, and imines. These results show the general applicability of this method for the synthesis of various amines.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carbon materials, whose structural and electronic properties can be fine-tuned, are promising material solutions for many energy-related systems. However, due to the lack of fundamental understanding of the carbon surface chemistry, especially when they are used in electrolytes, the rapid development of carbon as electrodes has led to many widely accepted misunderstandings. Focusing on the case of carbon-based electrode for water splitting, this Viewpoint tries to highlight the main problems of the area and demonstrates/presents the dynamic carbon surface chemistry in the application. The role of carbon as an anode for water splitting is revealed and if it can be practically used in water splitting is discussed.
{"title":"Can Carbon be Used as an Anode for Water Splitting?","authors":"Jiali Sun, Yuying Dang, Xiaoyan Sun, Saskia Heumann, Yuxiao Ding","doi":"10.1002/cssc.202401340","DOIUrl":"https://doi.org/10.1002/cssc.202401340","url":null,"abstract":"<p><p>Carbon materials, whose structural and electronic properties can be fine-tuned, are promising material solutions for many energy-related systems. However, due to the lack of fundamental understanding of the carbon surface chemistry, especially when they are used in electrolytes, the rapid development of carbon as electrodes has led to many widely accepted misunderstandings. Focusing on the case of carbon-based electrode for water splitting, this Viewpoint tries to highlight the main problems of the area and demonstrates/presents the dynamic carbon surface chemistry in the application. The role of carbon as an anode for water splitting is revealed and if it can be practically used in water splitting is discussed.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yen-Ming Li, Mohammadjafar Momeni, Huy Nguyen Dang Duc, Suvi von Bahder, Friedrich Roth, Wolfram Münchgesang, Manfred Danziger, Winfried Voitus, Dominik Nuss, Cornelia Sennewald, Tilmann Leisegang
A novel class of resource-efficient, woven-glass-grid current collectors (CCs) for Li-ion batteries is introduced. These CCs are based on ultra-light multifilament glass threads, woven to a grid and surrounded with a thin metal layer (equivalent to a 1 µm-thick metal foil) in a roll-to-roll physical vapor deposition process. This saves > 90% of the required Cu and Al metals and reduces the mass of the CCs by > 80%. At the same time, the gravimetric capacity of anodes with graphite and cathodes with LiCoO2 active material increases by 48% and 14%, respectively, while full cells are characterized by an increase of 26%. Thus, the specific energy can be improved by 25%. A complete anode and cathode fabrication process from preparing the CCs and electrodes to cells is described and demonstrated in coin cell format. Coin cells with woven-glass-grid CCs achieved 300 cycles with a capacity retention of 93%, a Coulombic efficiency of > 99.9%, and a higher rate capability until a C-rate of 3C. This technology opens up new possibilities for designing ultralight CCs with dedicated surface properties for Li and beyond Li batteries.
本文介绍了一类新型的资源节约型锂离子电池用玻璃编织栅集流器(CC)。这些 CC 以超轻多丝玻璃丝为基础,通过卷对卷物理气相沉积工艺编织成栅格,并在其周围镀上一层薄金属(相当于 1 µm 厚的金属箔)。这样可以节省 > 90% 所需的铜和铝金属,并将 CC 的质量减少 > 80%。同时,使用石墨的阳极和使用钴酸锂活性材料的阴极的重力容量分别增加了 48% 和 14%,而完整电池的重力容量增加了 26%。因此,比能量可提高 25%。本文介绍了从制备 CC 和电极到电池的完整阳极和阴极制造工艺,并以纽扣电池的形式进行了演示。采用玻璃编织栅 CC 的纽扣电池在循环 300 次后,容量保持率达到 93%,库仑效率大于 99.9%,并具有更高的速率能力,直到 C 速率达到 3C。这项技术为设计具有锂电池和超锂电池专用表面特性的超轻 CC 提供了新的可能性。
{"title":"Resource-efficient electrodes with metallized woven-glass-grid current collectors for lithium-ion batteries.","authors":"Yen-Ming Li, Mohammadjafar Momeni, Huy Nguyen Dang Duc, Suvi von Bahder, Friedrich Roth, Wolfram Münchgesang, Manfred Danziger, Winfried Voitus, Dominik Nuss, Cornelia Sennewald, Tilmann Leisegang","doi":"10.1002/cssc.202402233","DOIUrl":"https://doi.org/10.1002/cssc.202402233","url":null,"abstract":"<p><p>A novel class of resource-efficient, woven-glass-grid current collectors (CCs) for Li-ion batteries is introduced. These CCs are based on ultra-light multifilament glass threads, woven to a grid and surrounded with a thin metal layer (equivalent to a 1 µm-thick metal foil) in a roll-to-roll physical vapor deposition process. This saves > 90% of the required Cu and Al metals and reduces the mass of the CCs by > 80%. At the same time, the gravimetric capacity of anodes with graphite and cathodes with LiCoO2 active material increases by 48% and 14%, respectively, while full cells are characterized by an increase of 26%. Thus, the specific energy can be improved by 25%. A complete anode and cathode fabrication process from preparing the CCs and electrodes to cells is described and demonstrated in coin cell format. Coin cells with woven-glass-grid CCs achieved 300 cycles with a capacity retention of 93%, a Coulombic efficiency of > 99.9%, and a higher rate capability until a C-rate of 3C. This technology opens up new possibilities for designing ultralight CCs with dedicated surface properties for Li and beyond Li batteries.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ningning Zhang, Viktoria Lahmann, Jan Philipp Bittner, Pablo Domínguez de María, Sven Jakobtorweihen, Irina Smirnova, Selin Kara
Redox biocatalysis is an important pillar of the chemical industry. Yet, the enzymes' nature restricts most reactions to aqueous conditions, where the limited substrate solubility leads to unsustainable diluted biotranformations. Non-aqueous media represent a strategic solution to conduct intensified biocatalytic routes. Deep eutectic solvents (DESs) are designable solvents that can be customized to meet specific application needs. Within the large design space of combining DES components (and ratios), hydrophobic DESs hold the potential to be both enzyme-compatible - keeping the enzymes' hydration -, and solubilizers for hydrophobic reactants. We explored two hydrophobic DESs, lidocaine/oleic acid, and lidocaine/decanoic acid, as reaction media for carbonyl reduction catalyzed by horse liver alcohol dehydrogenase, focusing on the effect of water contents and on maximizing substrate loadings. Enzymes remained highly active and stable in the DESs with 20 wt.% buffer, whereas the reaction performance in DESs outperformed the pure buffer system with hydrophobic substrates (e.g., cinnamaldehyde to form the industrially relevant cinnamyl alcohol), with a 2-fold higher specific activity. Notably, the cinnamaldehyde reduction was for the first time performed at 800 mM (~100 g[[EQUATION]]L-1) with full conversion, which opens up new avenues to industrial applications of hydrophobic DESs for enzyme catalysis.
氧化还原生物催化是化学工业的重要支柱。然而,酶的特性限制了大多数反应在水性条件下进行,而水性条件下有限的底物溶解度会导致不可持续的稀释生物转化。非水介质是进行强化生物催化路线的战略解决方案。深共晶溶剂(DES)是一种可设计的溶剂,可根据具体应用需求进行定制。在结合 DES 成分(和比率)的巨大设计空间内,疏水性 DES 有可能既与酶兼容(保持酶的水合作用),又是疏水性反应物的增溶剂。我们探索了两种疏水性 DES(利多卡因/油酸和利多卡因/癸酸)作为马肝醇脱氢酶催化羰基还原的反应介质,重点研究了含水量的影响和底物负载的最大化。酶在含20 wt.%缓冲液的DES中保持高活性和稳定性,而在DES中的反应性能优于含疏水底物(如肉桂醛形成工业相关的肉桂醇)的纯缓冲液体系,比活性高出2倍。值得注意的是,肉桂醛还原首次在800 mM(约100 g[[方程]]L-1)的条件下实现了完全转化,这为疏水性DES在酶催化方面的工业应用开辟了新途径。
{"title":"Redox Biocatalysis in Lidocaine-based Hydrophobic Deep Eutectic Solvents: Non-conventional Media Outperform Aqueous Conditions.","authors":"Ningning Zhang, Viktoria Lahmann, Jan Philipp Bittner, Pablo Domínguez de María, Sven Jakobtorweihen, Irina Smirnova, Selin Kara","doi":"10.1002/cssc.202402075","DOIUrl":"https://doi.org/10.1002/cssc.202402075","url":null,"abstract":"<p><p>Redox biocatalysis is an important pillar of the chemical industry. Yet, the enzymes' nature restricts most reactions to aqueous conditions, where the limited substrate solubility leads to unsustainable diluted biotranformations. Non-aqueous media represent a strategic solution to conduct intensified biocatalytic routes. Deep eutectic solvents (DESs) are designable solvents that can be customized to meet specific application needs. Within the large design space of combining DES components (and ratios), hydrophobic DESs hold the potential to be both enzyme-compatible - keeping the enzymes' hydration -, and solubilizers for hydrophobic reactants. We explored two hydrophobic DESs, lidocaine/oleic acid, and lidocaine/decanoic acid, as reaction media for carbonyl reduction catalyzed by horse liver alcohol dehydrogenase, focusing on the effect of water contents and on maximizing substrate loadings. Enzymes remained highly active and stable in the DESs with 20 wt.% buffer, whereas the reaction performance in DESs outperformed the pure buffer system with hydrophobic substrates (e.g., cinnamaldehyde to form the industrially relevant cinnamyl alcohol), with a 2-fold higher specific activity. Notably, the cinnamaldehyde reduction was for the first time performed at 800 mM (~100 g[[EQUATION]]L-1) with full conversion, which opens up new avenues to industrial applications of hydrophobic DESs for enzyme catalysis.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}