Pub Date : 2024-11-01DOI: 10.1021/acssuschemeng.4c0639410.1021/acssuschemeng.4c06394
Yixuan Feng, Richard L. Smith Jr., Feng Shen* and Xinhua Qi*,
Quantitative conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to downstream chemicals at room temperature is a critical milestone in sustainable chemistry. Herein, conversion of metal–organic framework (MOF) structures into layered double hydroxide (LDH) electrocatalytic materials (NiFe-LDH/MOF) was fabricated using NiFe-MOF as a structure-oriented sacrificial template via an in situ electrochemical strategy. Results showed that the electrochemical method to convert the material structures not only overcame inherent limitations of MOF structures (inaccessible sites and low conductivity) but also eliminated LDH self-stacking. Hierarchical NiFe-LDH/MOF exhibited high catalytic activity and selectivity in the electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), which is due to the increased number of catalytically active sites and the extended electron transport channels of uniformly dispersed LDH nanosheets. Optimized Ni2Fe1-LDH/MOF materials achieved FDCA yields of 99% with Faraday efficiencies of 99% in 1 M KOH with 50 mM HMF at an applied potential of 1.40 V vs reversible hydrogen electrode at ambient temperature. This work demonstrates a promising method for fabricating LDH electrocatalytic materials from MOF structures and shows a proof of principle for selective oxidation of HMF to FDCA.
{"title":"Structure-Oriented Electrochemical Synthesis of Layered Double Hydroxide Electrocatalytic Materials for 5-Hydroxymethylfurfural Oxidation","authors":"Yixuan Feng, Richard L. Smith Jr., Feng Shen* and Xinhua Qi*, ","doi":"10.1021/acssuschemeng.4c0639410.1021/acssuschemeng.4c06394","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06394https://doi.org/10.1021/acssuschemeng.4c06394","url":null,"abstract":"<p >Quantitative conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to downstream chemicals at room temperature is a critical milestone in sustainable chemistry. Herein, conversion of metal–organic framework (MOF) structures into layered double hydroxide (LDH) electrocatalytic materials (NiFe-LDH/MOF) was fabricated using NiFe-MOF as a structure-oriented sacrificial template via an in situ electrochemical strategy. Results showed that the electrochemical method to convert the material structures not only overcame inherent limitations of MOF structures (inaccessible sites and low conductivity) but also eliminated LDH self-stacking. Hierarchical NiFe-LDH/MOF exhibited high catalytic activity and selectivity in the electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), which is due to the increased number of catalytically active sites and the extended electron transport channels of uniformly dispersed LDH nanosheets. Optimized Ni<sub>2</sub>Fe<sub>1</sub>-LDH/MOF materials achieved FDCA yields of 99% with Faraday efficiencies of 99% in 1 M KOH with 50 mM HMF at an applied potential of 1.40 V vs reversible hydrogen electrode at ambient temperature. This work demonstrates a promising method for fabricating LDH electrocatalytic materials from MOF structures and shows a proof of principle for selective oxidation of HMF to FDCA.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"12 46","pages":"16905–16913 16905–16913"},"PeriodicalIF":7.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1021/acssuschemeng.4c06416
Jingfeng Wu, Canhao Hua, Shenliang Hou, Jie Pan, Lingjun Zhu, Shurong Wang
Hydrodeoxygenation (HDO) plays a crucial role in the production of high-energy liquid fuels from lignin-derived phenols. Polyoxometalates (POMs), as strong acidic materials, are potential catalysts for liquid-phase HDO. In this study, we synthesized a series of Ru-based polyoxometalate catalysts (Ru/POMs) for the conversion of lignin-derived phenols to cycloalkanes. The optimization of Ru/POMs was achieved by controlling the ion types and ratios. The results indicated that the physiochemical properties of POMs were significantly influenced by the types of polyanions and metal cations, while the acidity related to the deoxygenation ability was greatly affected by the ion ratios of cations and polyanions. Additionally, the interaction between POMs and Ru varied depending on the type of POMs, leading to different Ru dispersions and hydrogenation ability. Among all catalysts tested, Ru/Cs2.5SiW exhibited superior catalytic performance due to its high Ru dispersion and appropriate acidity. Under optimal conditions (160 °C, 4 h, and 3 MPa of H2), guaiacol was completely converted to 93.7% cyclohexane in dodecane solvent. It was observed that Cs2.5SiW displayed high activity in C–O bond hydrogenolysis. This work successfully achieved efficient HDO of lignin-derived phenols and provided a strategy for designing polyoxometalate catalysts.
{"title":"Efficient C–O Bond Hydrogenolysis Over Polyoxometalate Catalysts in Mild Hydrodeoxygenation of Lignin-Derived Phenols to Cycloalkanes","authors":"Jingfeng Wu, Canhao Hua, Shenliang Hou, Jie Pan, Lingjun Zhu, Shurong Wang","doi":"10.1021/acssuschemeng.4c06416","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06416","url":null,"abstract":"Hydrodeoxygenation (HDO) plays a crucial role in the production of high-energy liquid fuels from lignin-derived phenols. Polyoxometalates (POMs), as strong acidic materials, are potential catalysts for liquid-phase HDO. In this study, we synthesized a series of Ru-based polyoxometalate catalysts (Ru/POMs) for the conversion of lignin-derived phenols to cycloalkanes. The optimization of Ru/POMs was achieved by controlling the ion types and ratios. The results indicated that the physiochemical properties of POMs were significantly influenced by the types of polyanions and metal cations, while the acidity related to the deoxygenation ability was greatly affected by the ion ratios of cations and polyanions. Additionally, the interaction between POMs and Ru varied depending on the type of POMs, leading to different Ru dispersions and hydrogenation ability. Among all catalysts tested, Ru/Cs<sub>2.5</sub>SiW exhibited superior catalytic performance due to its high Ru dispersion and appropriate acidity. Under optimal conditions (160 °C, 4 h, and 3 MPa of H<sub>2</sub>), guaiacol was completely converted to 93.7% cyclohexane in dodecane solvent. It was observed that Cs<sub>2.5</sub>SiW displayed high activity in C–O bond hydrogenolysis. This work successfully achieved efficient HDO of lignin-derived phenols and provided a strategy for designing polyoxometalate catalysts.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ecofriendly and renewable properties are highly desirable for separators of lithium batteries, apart from the notorious safety issues. As a natural polysaccharide material, sodium alginate (SA) has outstanding biodegradability and biocompatibility and has usually been used for the binder of electrodes due to its high ionic conductivity. Herein, SA porous separators were initially prepared by a facile polymer-assisted phase separation in which polyethylene glycol (PEG) and acetonitrile acted as a pore-forming agent and an extraction solvent, respectively. The influence of PEG content on the pore formation was systematically investigated, and the uniform and continuous pore structures were successfully realized at the PEG content of 200–500 wt %. Additionally, the cellulose-based paper support (KP) and poly(vinylidene fluoride-co-hexafluoropropylene) porous coating (PVH) were adopted for the decent mechanical integrity of SA porous membranes. The prepared SA composite separators showed excellent thermal dimensional stability, high porosity, and good electrolyte wettability. Moreover, the polar features of SA endowed the composite separators with high ionic conductivity (4.8 mS cm–1) and lithium ion transference number (0.62). The strong depression capacity of lithium dendrites and a comparable electrochemical performance were also observed for the SA-based separators compared with the pure KP and commercial polyolefin separators.
除了众所周知的安全问题外，生态友好和可再生的特性也是锂电池隔膜非常需要的。作为一种天然多糖材料，海藻酸钠（SA）具有出色的生物降解性和生物相容性，由于其离子传导性高，通常被用于电极粘合剂。本文通过聚合物辅助相分离法初步制备了海藻酸钠多孔分离器，其中聚乙二醇（PEG）和乙腈分别作为成孔剂和萃取溶剂。系统研究了 PEG 含量对孔隙形成的影响，当 PEG 含量为 200-500 wt % 时，成功实现了均匀连续的孔隙结构。此外，为了保证 SA 多孔膜的机械完整性，还采用了纤维素基纸支撑（KP）和聚偏氟乙烯-六氟丙烯多孔涂层（PVH）。制备的 SA 复合分离器具有优异的热尺寸稳定性、高孔隙率和良好的电解质润湿性。此外，SA 的极性特征还赋予了复合隔膜较高的离子电导率（4.8 mS cm-1）和锂离子转移数（0.62）。与纯 KP 和商用聚烯烃隔膜相比，基于 SA 的隔膜还具有很强的锂枝晶抑制能力和可比的电化学性能。
{"title":"Paper-Supported Sodium Alginate Composite Separator Prepared by Polymer-Assisted Phase Separation for Lithium Ion Batteries","authors":"Pingping Chen, Anqi Chen, Ge Li, Zhongzheng Yang, Yu Liu, Qinghui Zeng, Liaoyun Zhang","doi":"10.1021/acssuschemeng.4c06833","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06833","url":null,"abstract":"Ecofriendly and renewable properties are highly desirable for separators of lithium batteries, apart from the notorious safety issues. As a natural polysaccharide material, sodium alginate (SA) has outstanding biodegradability and biocompatibility and has usually been used for the binder of electrodes due to its high ionic conductivity. Herein, SA porous separators were initially prepared by a facile polymer-assisted phase separation in which polyethylene glycol (PEG) and acetonitrile acted as a pore-forming agent and an extraction solvent, respectively. The influence of PEG content on the pore formation was systematically investigated, and the uniform and continuous pore structures were successfully realized at the PEG content of 200–500 wt %. Additionally, the cellulose-based paper support (KP) and poly(vinylidene fluoride-<i>co</i>-hexafluoropropylene) porous coating (PVH) were adopted for the decent mechanical integrity of SA porous membranes. The prepared SA composite separators showed excellent thermal dimensional stability, high porosity, and good electrolyte wettability. Moreover, the polar features of SA endowed the composite separators with high ionic conductivity (4.8 mS cm<sup>–1</sup>) and lithium ion transference number (0.62). The strong depression capacity of lithium dendrites and a comparable electrochemical performance were also observed for the SA-based separators compared with the pure KP and commercial polyolefin separators.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-31DOI: 10.1021/acssuschemeng.4c07543
Silvia Rizzo, Ana Toplak, Marco Macis, Lucia Ferrazzano, Antonio Ricci, Alessandra Tolomelli, Walter Cabri
The development of green approaches to peptide synthesis is essential, as peptides are gaining prominence in the pharmaceutical market. Traditional methods often involve harmful solvents and high energy use, prompting a shift toward sustainable and eco-friendly alternatives. Liraglutide, a GLP-1 analogue used in the treatment of obesity and type-2 diabetes, has been synthesized through a hybrid chemo-enzymatic approach (CEPS), taking advantage of green solvent mixtures in the synthesis of peptide fragments and of selectivity of a ligase enzyme for their coupling. This method offers great advantages both in the quality of the upstream wastes and in the reduction of solvent volumes in downstream purification, together with the high purity of the target liraglutide.
{"title":"A Sustainable Chemo-Enzymatic Approach to the Synthesis of Liraglutide","authors":"Silvia Rizzo, Ana Toplak, Marco Macis, Lucia Ferrazzano, Antonio Ricci, Alessandra Tolomelli, Walter Cabri","doi":"10.1021/acssuschemeng.4c07543","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07543","url":null,"abstract":"The development of green approaches to peptide synthesis is essential, as peptides are gaining prominence in the pharmaceutical market. Traditional methods often involve harmful solvents and high energy use, prompting a shift toward sustainable and eco-friendly alternatives. Liraglutide, a GLP-1 analogue used in the treatment of obesity and type-2 diabetes, has been synthesized through a hybrid chemo-enzymatic approach (CEPS), taking advantage of green solvent mixtures in the synthesis of peptide fragments and of selectivity of a ligase enzyme for their coupling. This method offers great advantages both in the quality of the upstream wastes and in the reduction of solvent volumes in downstream purification, together with the high purity of the target liraglutide.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"40 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-31DOI: 10.1021/acssuschemeng.4c07543
Silvia Rizzo, Ana Toplak, Marco Macis, Lucia Ferrazzano, Antonio Ricci, Alessandra Tolomelli, Walter Cabri
The development of green approaches to peptide synthesis is essential, as peptides are gaining prominence in the pharmaceutical market. Traditional methods often involve harmful solvents and high energy use, prompting a shift toward sustainable and eco-friendly alternatives. Liraglutide, a GLP-1 analogue used in the treatment of obesity and type-2 diabetes, has been synthesized through a hybrid chemo-enzymatic approach (CEPS), taking advantage of green solvent mixtures in the synthesis of peptide fragments and of selectivity of a ligase enzyme for their coupling. This method offers great advantages both in the quality of the upstream wastes and in the reduction of solvent volumes in downstream purification, together with the high purity of the target liraglutide.
{"title":"A Sustainable Chemo-Enzymatic Approach to the Synthesis of Liraglutide","authors":"Silvia Rizzo, Ana Toplak, Marco Macis, Lucia Ferrazzano, Antonio Ricci, Alessandra Tolomelli, Walter Cabri","doi":"10.1021/acssuschemeng.4c07543","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07543","url":null,"abstract":"The development of green approaches to peptide synthesis is essential, as peptides are gaining prominence in the pharmaceutical market. Traditional methods often involve harmful solvents and high energy use, prompting a shift toward sustainable and eco-friendly alternatives. Liraglutide, a GLP-1 analogue used in the treatment of obesity and type-2 diabetes, has been synthesized through a hybrid chemo-enzymatic approach (CEPS), taking advantage of green solvent mixtures in the synthesis of peptide fragments and of selectivity of a ligase enzyme for their coupling. This method offers great advantages both in the quality of the upstream wastes and in the reduction of solvent volumes in downstream purification, together with the high purity of the target liraglutide.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-31DOI: 10.1021/acssuschemeng.4c06869
Qianpeng Jin, Simeng Gao, Yuchi Wang, Zongyi Qin
The development of aqueous zinc–iodine (Zn–I2) batteries is plagued by long-term cycling stability, mainly caused by limited iodine loading, polyiodide shuttle, and uneven Zn2+ deposition. Herein, a unique tree-ring-like hierarchical structure constructed by polyaniline (PANI) nanofiber arrays and reduced graphene oxide (RGO) was designed to provide the nanopore array for prestoring iodine ions and confine the iodine conversion reaction as well as promote electron and ion transport along PANI nanofibers, thereby enhancing the capacity and cycling durability of Zn–I2 batteries. Meanwhile, the sulfonic polyacrylamide/glycerol (SPAM/Gly) hydrogel electrolyte containing the ZnI2 additive is introduced for simultaneously inhibiting the polyiodide shuttle and side reactions on the Zn anode accompanied by excellent antifreezing properties and flexibility. As a result, the assembled flexible battery realized a remarkable areal capacity of 2.3 mAh·cm–2 at 0.5 mA·cm–2 (corresponding to 287.5 mAh·g–1) and a maximum energy density of 2.54 mWh·cm–2 at a high mass loading of 8 mg·cm–2. Consequently, the battery still exhibited a capacity of 0.784 mAh·cm–2 over 6000 cycles and 0.98 mAh·cm–2 after 200 cycles under −20 °C at 2 mA·cm–2. Such flexible device also maintains a steady supply of powering electronic gadget during deformations.
{"title":"Synergistic Construction of Hierarchical Tree-Ring Structures and Blocked Interfaces for Stable, Flexible Zinc–Iodine Batteries with Ultrahigh Areal/Gravimetric Capacity","authors":"Qianpeng Jin, Simeng Gao, Yuchi Wang, Zongyi Qin","doi":"10.1021/acssuschemeng.4c06869","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06869","url":null,"abstract":"The development of aqueous zinc–iodine (Zn–I<sub>2</sub>) batteries is plagued by long-term cycling stability, mainly caused by limited iodine loading, polyiodide shuttle, and uneven Zn<sup>2+</sup> deposition. Herein, a unique tree-ring-like hierarchical structure constructed by polyaniline (PANI) nanofiber arrays and reduced graphene oxide (RGO) was designed to provide the nanopore array for prestoring iodine ions and confine the iodine conversion reaction as well as promote electron and ion transport along PANI nanofibers, thereby enhancing the capacity and cycling durability of Zn–I<sub>2</sub> batteries. Meanwhile, the sulfonic polyacrylamide/glycerol (SPAM/Gly) hydrogel electrolyte containing the ZnI<sub>2</sub> additive is introduced for simultaneously inhibiting the polyiodide shuttle and side reactions on the Zn anode accompanied by excellent antifreezing properties and flexibility. As a result, the assembled flexible battery realized a remarkable areal capacity of 2.3 mAh·cm<sup>–2</sup> at 0.5 mA·cm<sup>–2</sup> (corresponding to 287.5 mAh·g<sup>–1</sup>) and a maximum energy density of 2.54 mWh·cm<sup>–2</sup> at a high mass loading of 8 mg·cm<sup>–2</sup>. Consequently, the battery still exhibited a capacity of 0.784 mAh·cm<sup>–2</sup> over 6000 cycles and 0.98 mAh·cm<sup>–2</sup> after 200 cycles under −20 °C at 2 mA·cm<sup>–2</sup>. Such flexible device also maintains a steady supply of powering electronic gadget during deformations.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-30DOI: 10.1021/acssuschemeng.4c04317
Joseph Jegan Roy, Ernest Jun Jie Tang, Bin Cao, Madhavi Srinivasan
Lithium-ion batteries (LIBs) power most electronic devices, electric vehicles (EVs), and energy storage devices, and LIB waste is the most critical global problem in electronic waste management. However, recovering and reusing metals from discarded LIBs can reduce environmental risks and provide valuable sources of metal for new batteries. Food waste is a global issue. Most food leftovers are discarded in landfills or incinerated, with a recycling rate of approximately 10–20%. Utilizing food waste to treat LIB waste is an innovative approach that can effectively reduce waste and promote a circular economy, leading to sustainable expansion. In this innovative and environmentally friendly study, we utilize a biocatalytic procedure to transform food waste into lixiviants and extract valuable metals such as Ni, Mn, Co, and Li from spent LIBs. This study also demonstrates that gluconic acid is the primary acid produced through the enzymatic conversion of food waste into lixiviants, a sustainable process that selectively forms metal chelates with valuable LIB metals. The food-waste-derived lixiviants could extract valuable metals from LCO- and NMC-based industrial black masses at a solid content of 50 g/L with a leaching efficiency of 80–99% confirmed by inductively coupled plasma optical emission spectrometry (ICP-OES). The X-ray diffraction, scanning electron microscopy, and ICP-OES studies of LIB black masses and their leaching residues have verified that nearly all metals have been extracted from the LIB black mass. This environmentally conscious approach can efficiently extract metals from exhausted EV batteries in the interest of sustainability.
{"title":"Metal Extraction from Commercial Black Mass of Spent Lithium-Ion Batteries Using Food-Waste-Derived Lixiviants through a Biological Process","authors":"Joseph Jegan Roy, Ernest Jun Jie Tang, Bin Cao, Madhavi Srinivasan","doi":"10.1021/acssuschemeng.4c04317","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04317","url":null,"abstract":"Lithium-ion batteries (LIBs) power most electronic devices, electric vehicles (EVs), and energy storage devices, and LIB waste is the most critical global problem in electronic waste management. However, recovering and reusing metals from discarded LIBs can reduce environmental risks and provide valuable sources of metal for new batteries. Food waste is a global issue. Most food leftovers are discarded in landfills or incinerated, with a recycling rate of approximately 10–20%. Utilizing food waste to treat LIB waste is an innovative approach that can effectively reduce waste and promote a circular economy, leading to sustainable expansion. In this innovative and environmentally friendly study, we utilize a biocatalytic procedure to transform food waste into lixiviants and extract valuable metals such as Ni, Mn, Co, and Li from spent LIBs. This study also demonstrates that gluconic acid is the primary acid produced through the enzymatic conversion of food waste into lixiviants, a sustainable process that selectively forms metal chelates with valuable LIB metals. The food-waste-derived lixiviants could extract valuable metals from LCO- and NMC-based industrial black masses at a solid content of 50 g/L with a leaching efficiency of 80–99% confirmed by inductively coupled plasma optical emission spectrometry (ICP-OES). The X-ray diffraction, scanning electron microscopy, and ICP-OES studies of LIB black masses and their leaching residues have verified that nearly all metals have been extracted from the LIB black mass. This environmentally conscious approach can efficiently extract metals from exhausted EV batteries in the interest of sustainability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mn-rich ternary cathodes are highly regarded as a potential option for sodium-ion batteries (SIBs) due to their low cost and high theoretical capacity. Nonetheless, cycling stability was hindered by the occurrence of high-voltage phase transitions. In this work, Na0.67(Ni0.1Mn0.8Fe0.1)1–xMgxO2 (NaNMF-Mgx) cathode materials with high-voltage zero-phase transitions property were successfully synthesized. Amazingly, it was found that there was a valuable strengthening in the occupancy of stabler Nae sites by employing the Mg-doping strategy; and the calculation highlighted excellent structural stability and conductivity of NaNMF-Mg0.04, which has the lowest thermodynamic formation energy and a narrow band gap. The combination of theory and experiment demonstrated the underlying mechanisms of Mg substitution. Especially, Mg doping had the potential to regulate Nae/Naf ratio, and the ratio of NaNMF-Mg0.04 reached the maximum, indicating its most remarkable “rich-Nae” effect. Moreover, ex-situ XRD and ADF-STEM certified that NaNMF-Mg0.04 cathode maintained an intact P2 phase structure during high-voltage charging process. The “rich-Nae” and “zero-phase transitions” effects enabled NaNMF-Mg0.04 cathode to express remarkable initial capacitance (119.5 mAh g–1, 0.1 C), stability (80.0% over 200 cycles), and energy density (356.5 Wh kg–1). This unique mechanism provided fresh insights into revisiting the relationship between structure and performance and might open up a new idea for designing novel Mn-rich ternary cathodes with zero-phase transitions property in the future.
{"title":"Properties of Rich-Nae Effect and Zero-Phase Transition in P2–Na0.67(Ni0.1Mn0.8Fe0.1)1–xMgxO2 Cathodes for Rapid and Stable Sodium Storage","authors":"Rui Huang, Shaohua Luo, Pengyu Li, Qi Sun, Guodong Hao, Jie Feng, Lixiong Qian, Shengxue Yan, Jing Guo","doi":"10.1021/acssuschemeng.4c07004","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07004","url":null,"abstract":"Mn-rich ternary cathodes are highly regarded as a potential option for sodium-ion batteries (SIBs) due to their low cost and high theoretical capacity. Nonetheless, cycling stability was hindered by the occurrence of high-voltage phase transitions. In this work, Na<sub>0.67</sub>(Ni<sub>0.1</sub>Mn<sub>0.8</sub>Fe<sub>0.1</sub>)<sub>1–<i>x</i></sub>Mg<sub><i>x</i></sub>O<sub>2</sub> (NaNMF-Mg<i>x</i>) cathode materials with high-voltage zero-phase transitions property were successfully synthesized. Amazingly, it was found that there was a valuable strengthening in the occupancy of stabler Na<sub>e</sub> sites by employing the Mg-doping strategy; and the calculation highlighted excellent structural stability and conductivity of NaNMF-Mg0.04, which has the lowest thermodynamic formation energy and a narrow band gap. The combination of theory and experiment demonstrated the underlying mechanisms of Mg substitution. Especially, Mg doping had the potential to regulate Na<sub>e</sub>/Na<sub>f</sub> ratio, and the ratio of NaNMF-Mg0.04 reached the maximum, indicating its most remarkable “rich-Na<sub>e</sub>” effect. Moreover, ex-situ XRD and ADF-STEM certified that NaNMF-Mg0.04 cathode maintained an intact P2 phase structure during high-voltage charging process. The “rich-Na<sub>e</sub>” and “zero-phase transitions” effects enabled NaNMF-Mg0.04 cathode to express remarkable initial capacitance (119.5 mAh g<sup>–1</sup>, 0.1 C), stability (80.0% over 200 cycles), and energy density (356.5 Wh kg<sup>–1</sup>). This unique mechanism provided fresh insights into revisiting the relationship between structure and performance and might open up a new idea for designing novel Mn-rich ternary cathodes with zero-phase transitions property in the future.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-30DOI: 10.1021/acssuschemeng.4c07937
Yi Zhang, Fang Liu, Jun Zhang, Wenqi Gao, Jian Yu, Lei Wang
Some inconsistencies were recently discovered in our previously published article due to the upload of a wrong version of the Supporting Information. The scientific discoveries and conclusions in the original paper are not affected. A corrected version of the Supporting Information is provided. The Supporting Information includes methodologies from USEtox and aquatic ecotoxicity experiments of AmimCl and EmimOAc, life cycle inventories of 3 ILs' precursors and results of sensitivity and scenario analyses. Correction to Figure 4: We have corrected the labeling error of the CFeco value for EmimOAc. The corrected CFeco value for the freshwater ecotoxicity of emitted EmimOAc is 229.33 PAF m3 d/kg emitted, which is consistent with the value stated in the main text. Correction of SI Section Numbering Error in the Main Text: In the Section “IL Contribution and Comparative Analyses” of the main text, the Supporting Information S5 should be labeled as Supporting Information S6, while the Supporting Information S6 should be labeled as Supporting Information S5. Addition to SI Section 3 (Table S1): We have added descriptions of the USEtox input parameters in Table S1 along with their data sources. Addition to SI Section 4 (Table S2): We have replaced the original Table S2 with the latest version. Figure 4. CFs for freshwater emissions for AmimCl, BmimCl, and EmimOAc. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.4c07937. Calculation methodology and mandatory input data of 3 ILs for USEtox model; toxicity test of AmimCl and EmimOAc; LCI and sensitivity analysis of precursor 1-methylimidazole and 1-ethylimidazole; scenario analysis of EmimOAc alternative synthesis pathway and detailed calculation for relative LCI unavailable precursors; and ranking principle of CHEM21 selection guide (PDF) Correction to “Life Cycle Thinking-Based GREENNESS Framework for Advancing Green Chemistry: Case Study with Typical Ionic Liquids for Cellulose Dissolution and Regeneration” 3 views 0 shares 0 downloads Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.
{"title":"Correction to “Life Cycle Thinking-Based GREENNESS Framework for Advancing Green Chemistry: Case Study with Typical Ionic Liquids for Cellulose Dissolution and Regeneration”","authors":"Yi Zhang, Fang Liu, Jun Zhang, Wenqi Gao, Jian Yu, Lei Wang","doi":"10.1021/acssuschemeng.4c07937","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07937","url":null,"abstract":"Some inconsistencies were recently discovered in our previously published article due to the upload of a wrong version of the Supporting Information. The scientific discoveries and conclusions in the original paper are not affected. A corrected version of the Supporting Information is provided. The Supporting Information includes methodologies from USEtox and aquatic ecotoxicity experiments of AmimCl and EmimOAc, life cycle inventories of 3 ILs' precursors and results of sensitivity and scenario analyses. <b>Correction to</b> Figure 4<b>:</b> We have corrected the labeling error of the CF<sub>eco</sub> value for EmimOAc. The corrected CF<sub>eco</sub> value for the freshwater ecotoxicity of emitted EmimOAc is 229.33 PAF m<sup>3</sup> d/kg emitted, which is consistent with the value stated in the main text. <b>Correction of SI Section Numbering Error in the Main Text:</b> In the Section “IL Contribution and Comparative Analyses” of the main text, the Supporting Information S5 should be labeled as Supporting Information S6, while the Supporting Information S6 should be labeled as Supporting Information S5. <b>Addition to SI Section 3 (Table S1):</b> We have added descriptions of the USEtox input parameters in Table S1 along with their data sources. <b>Addition to SI Section 4 (Table S2):</b> We have replaced the original Table S2 with the latest version. Figure 4. <i>CF</i>s for freshwater emissions for AmimCl, BmimCl, and EmimOAc. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.4c07937. Calculation methodology and mandatory input data of 3 ILs for USEtox model; toxicity test of AmimCl and EmimOAc; LCI and sensitivity analysis of precursor 1-methylimidazole and 1-ethylimidazole; scenario analysis of EmimOAc alternative synthesis pathway and detailed calculation for relative LCI unavailable precursors; and ranking principle of CHEM21 selection guide (PDF) Correction to “Life Cycle Thinking-Based GREENNESS\u0000Framework for Advancing Green Chemistry: Case Study with Typical Ionic\u0000Liquids for Cellulose Dissolution and Regeneration” <span> 3 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"112 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Recyclable ionic liquid–catalyzed tandem annulation of alkyl lactates has been demonstrated, enabling divergent synthesis of dihydroquinoxalines and quinoxalines as a function of reaction time. Notably, dihydroquinoxalines could be furnished swiftly at room temperature with high yields. More significantly, the tunable synthesis is exemplified by repeatably stopping–restarting processes. Furthermore, biological studies indicate that dihydroquinoxalines with alkoxycarbonyl substitution at the C4 position are promising agrochemical candidates in terms of their antifungal activity. This method features the advantages of biomass utilization (RP > 75%), eco-benign manner (E-factor < 3), and the capacity for antileishmanial agent synthesis. Mechanistic studies established a kinetic preference for the formation of dihydroquinoxaline rather than quinoxaline through decarboxylation being thermodynamically favored. The current study reveals that reaction time could modulate the selective conversion of lactates and demonstrates the feasibility of the production of biologically valuable heterocycles from biomass.
{"title":"Ionic Liquid–Catalyzed Annulation of Biomass-Derived Alkyl Lactates: Time-Dependent Tunable Synthesis of Bioactive Dihydroquinoxalines and Quinoxalines","authors":"Shanshan Liu, Zhenzhen Li, Pingjun Zhang, Yaoyao Zhang, Weiwei Dong, Lin-Yu Jiao","doi":"10.1021/acssuschemeng.4c05755","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05755","url":null,"abstract":"Recyclable ionic liquid–catalyzed tandem annulation of alkyl lactates has been demonstrated, enabling divergent synthesis of dihydroquinoxalines and quinoxalines as a function of reaction time. Notably, dihydroquinoxalines could be furnished swiftly at room temperature with high yields. More significantly, the tunable synthesis is exemplified by repeatably stopping–restarting processes. Furthermore, biological studies indicate that dihydroquinoxalines with alkoxycarbonyl substitution at the C4 position are promising agrochemical candidates in terms of their antifungal activity. This method features the advantages of biomass utilization (RP > 75%), eco-benign manner (E-factor < 3), and the capacity for antileishmanial agent synthesis. Mechanistic studies established a kinetic preference for the formation of dihydroquinoxaline rather than quinoxaline through decarboxylation being thermodynamically favored. The current study reveals that reaction time could modulate the selective conversion of lactates and demonstrates the feasibility of the production of biologically valuable heterocycles from biomass.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"126 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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