Pub Date : 2024-12-16DOI: 10.1021/acssuschemeng.4c06557
Mengdan Tian, Chuanzheng Zhu, Kun Luo
Aqueous zinc-ion batteries (AZIBs) have attracted massive interest on account of their environmental friendliness, low price, and high security. Nevertheless, the application of AZIBs is seriously constrained by the high liquid–solid transition temperature of aqueous electrolytes, which is strongly related to the water network connected through hydrogen bonds (HBs). Another critical technical issue is to explore the appropriate electrode material compatible with a low-temperature aqueous electrolyte. In order to ensure the battery works properly at low-temperature conditions, a high-entropy electrolyte (HEE) with multicomponent perchlorate salts, (Zn, Ca, Mg, Li)ClO4, is developed. The calorimetric analysis indicates that the HEE exhibits an extremely low liquid–glass transition temperature (−114 °C). Structural characterizations using Raman, FTIR, and NMR spectroscopy indicate that the introduction of multicomponent perchlorate salts into the aqueous electrolyte breaks the initial water network by the formation of M···(H2O)n···ClO4– (M is Zn2+, Ca2+, Mg2+ or Li+) configurations, and the HEE therefore remains unfrozen even at −70 °C. The in situ viscosity measurement indicates the HEE has a viscosity of 13.8 mPa S at −70 °C. The electrochemical measurements indicate that the ionic conductivity of the HEE is 22.6 mS cm–1 at 25 °C and 2.7 mS cm–1 at −70 °C, and it has excellent electrochemical compatibility with Zn metal upon cycling Zn||Zn symmetric cells. The compatibility of the HEE and different electrode materials, particularly vanadate oxide with preinserted cations (KVO) and a carbon composite material with iodine (CCM/I2) in this study, is systematically investigated, and the results of electrochemical measurements indicate the HEE shows the selectivity of battery systems. The KVO|HEE|Zn battery exhibits poor cycling stability at room temperature (only 33 mA h g–1 after 5,000 cycles at 5.0 A g–1), while the CCM-I2|HEE|Zn battery displays a capacity of 182 mA h g–1 at 100 mA g–1 in the first cycle and superior cycling performances (102 mA h g–1 after 5,000 cycles at 5.0 A g–1). Low-temperature electrochemical measurements demonstrate that the battery system with the HEE exhibits enhanced electrochemical performances at −70 °C when compared with the binary electrolyte system (Zn, 3Ca)ClO4. This work reveals the significance of electrode/electrolyte adaptability on the electrochemical performances of AZIBs and provides valuable insights for constructing low-temperature electrolytes using a multicomponent high-entropy strategy.
锌离子水电池（AZIBs）因其环保、低价和高安全性而备受关注。然而，水溶液电解质的液固转换温度较高，这与通过氢键（HB）连接的水网络密切相关，严重制约了 AZIB 的应用。另一个关键技术问题是探索与低温水性电解质兼容的适当电极材料。为了确保电池在低温条件下正常工作，开发了一种含有多组分高氯酸盐（Zn、Ca、Mg、Li）ClO4 的高熵电解质（HEE）。量热分析表明，这种高熵电解质具有极低的液晶转变温度（-114 °C）。利用拉曼光谱、傅里叶变换红外光谱和核磁共振光谱进行的结构表征表明，在水性电解质中引入多组分高氯酸盐，通过形成 M----（H2O）n----ClO4--（M 为 Zn2+、Ca2+、Mg2+ 或 Li+）构型打破了最初的水网络，因此 HEE 即使在 -70 ℃ 下也不会冻结。原位粘度测量表明，HEE 在 -70 °C 时的粘度为 13.8 mPa S。电化学测量结果表明，HEE 在 25 °C 时的离子电导率为 22.6 mS cm-1，在 -70 °C 时的离子电导率为 2.7 mS cm-1。系统地研究了 HEE 与不同电极材料的兼容性，特别是本研究中预插入阳离子的氧化钒（KVO）和含碘的碳复合材料（CCM/I2），电化学测量结果表明 HEE 显示了电池系统的选择性。KVO|HEE|Zn 电池在室温下的循环稳定性较差（在 5.0 A g-1 条件下循环 5,000 次后只有 33 mA h g-1），而 CCM-I2|HEE|Zn 电池在第一次循环 100 mA g-1 时的容量为 182 mA h g-1，循环性能优越（在 5.0 A g-1 条件下循环 5,000 次后 102 mA h g-1）。低温电化学测量结果表明，与二元电解质体系（Zn, 3Ca)ClO4）相比，含有 HEE 的电池体系在 -70 °C 下具有更强的电化学性能。这项研究揭示了电极/电解质适应性对 AZIB 电化学性能的重要影响，并为采用多组分高熵策略构建低温电解质提供了宝贵的见解。
{"title":"Selective Compatibility of High-Entropy Electrolytes for Low-Temperature Aqueous Zinc–Iodine Batteries","authors":"Mengdan Tian, Chuanzheng Zhu, Kun Luo","doi":"10.1021/acssuschemeng.4c06557","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06557","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) have attracted massive interest on account of their environmental friendliness, low price, and high security. Nevertheless, the application of AZIBs is seriously constrained by the high liquid–solid transition temperature of aqueous electrolytes, which is strongly related to the water network connected through hydrogen bonds (HBs). Another critical technical issue is to explore the appropriate electrode material compatible with a low-temperature aqueous electrolyte. In order to ensure the battery works properly at low-temperature conditions, a high-entropy electrolyte (HEE) with multicomponent perchlorate salts, (Zn, Ca, Mg, Li)ClO<sub>4</sub>, is developed. The calorimetric analysis indicates that the HEE exhibits an extremely low liquid–glass transition temperature (−114 °C). Structural characterizations using Raman, FTIR, and NMR spectroscopy indicate that the introduction of multicomponent perchlorate salts into the aqueous electrolyte breaks the initial water network by the formation of M···(H<sub>2</sub>O)<sub><i>n</i></sub>···ClO<sub>4</sub><sup>–</sup> (M is Zn<sup>2+</sup>, Ca<sup>2+</sup>, Mg<sup>2+</sup> or Li<sup>+</sup>) configurations, and the HEE therefore remains unfrozen even at −70 °C. The in situ viscosity measurement indicates the HEE has a viscosity of 13.8 mPa S at −70 °C. The electrochemical measurements indicate that the ionic conductivity of the HEE is 22.6 mS cm<sup>–1</sup> at 25 °C and 2.7 mS cm<sup>–1</sup> at −70 °C, and it has excellent electrochemical compatibility with Zn metal upon cycling Zn||Zn symmetric cells. The compatibility of the HEE and different electrode materials, particularly vanadate oxide with preinserted cations (KVO) and a carbon composite material with iodine (CCM/I<sub>2</sub>) in this study, is systematically investigated, and the results of electrochemical measurements indicate the HEE shows the selectivity of battery systems. The KVO|HEE|Zn battery exhibits poor cycling stability at room temperature (only 33 mA h g<sup>–1</sup> after 5,000 cycles at 5.0 A g<sup>–1</sup>), while the CCM-I<sub>2</sub>|HEE|Zn battery displays a capacity of 182 mA h g<sup>–1</sup> at 100 mA g<sup>–1</sup> in the first cycle and superior cycling performances (102 mA h g<sup>–1</sup> after 5,000 cycles at 5.0 A g<sup>–1</sup>). Low-temperature electrochemical measurements demonstrate that the battery system with the HEE exhibits enhanced electrochemical performances at −70 °C when compared with the binary electrolyte system (Zn, 3Ca)ClO<sub>4</sub>. This work reveals the significance of electrode/electrolyte adaptability on the electrochemical performances of AZIBs and provides valuable insights for constructing low-temperature electrolytes using a multicomponent high-entropy strategy.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832666","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 : 2024-12-16DOI: 10.1021/acssuschemeng.4c07671
Qiankang Liao, You Wang, Chen Chen, Sai Zhang
The aqueous-phase reforming of the methanol (APRM) reaction provides a potential approach for hydrogen (H2) storage and transportation. However, the limited capacity of Pt nanocatalysts for H2O activation leads to the drawback of requiring high reaction temperatures (>200 °C) to achieve efficient H2 generation through the APRM reaction. Herein, the electronic density of Pt nanocatalysts has been regulated by the phase of the Al2O3 supports. Mechanism analysis revealed that the α-Al2O3 supports with larger lattice fringe spacing resulted in an enhanced electronic density of Pt nanocatalysts, thereby enabling the effective adsorption and activation of H2O. Consequently, the Pt/α-Al2O3 catalysts exhibited a TOF value of 69.8 h–1 at 30 °C for H2 generation via APRM reaction. Notably, this H2 generation rate even suppressed that achieved by previous state-of-the-art homogeneous catalysts. This finding presents a promising avenue toward flexible hydrogen utilization.
{"title":"Electronic Regulation of Pt for Low-Temperature Hydrogen Generation from Methanol and Water","authors":"Qiankang Liao, You Wang, Chen Chen, Sai Zhang","doi":"10.1021/acssuschemeng.4c07671","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07671","url":null,"abstract":"The aqueous-phase reforming of the methanol (APRM) reaction provides a potential approach for hydrogen (H<sub>2</sub>) storage and transportation. However, the limited capacity of Pt nanocatalysts for H<sub>2</sub>O activation leads to the drawback of requiring high reaction temperatures (>200 °C) to achieve efficient H<sub>2</sub> generation through the APRM reaction. Herein, the electronic density of Pt nanocatalysts has been regulated by the phase of the Al<sub>2</sub>O<sub>3</sub> supports. Mechanism analysis revealed that the α-Al<sub>2</sub>O<sub>3</sub> supports with larger lattice fringe spacing resulted in an enhanced electronic density of Pt nanocatalysts, thereby enabling the effective adsorption and activation of H<sub>2</sub>O. Consequently, the Pt/α-Al<sub>2</sub>O<sub>3</sub> catalysts exhibited a TOF value of 69.8 h<sup>–1</sup> at 30 °C for H<sub>2</sub> generation via APRM reaction. Notably, this H<sub>2</sub> generation rate even suppressed that achieved by previous state-of-the-art homogeneous catalysts. This finding presents a promising avenue toward flexible hydrogen utilization.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832665","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 : 2024-12-16DOI: 10.1021/acssuschemeng.4c05458
Abdullah, Sara Shakibania, Taral Patel, Divine Yufetar Shyntum, Katarzyna Krukiewicz
Shewanella oneidensis MR-1 is an electroactive bacterium commonly employed in the design of microbial fuel cells (MFCs) due to its ability to convert organic matter to electricity. Its applicability is limited by low adhesion to the surface of the electrode, which decreases the efficiency of charge transfer and reduces the available power outputs. In this study, we aimed to improve the adhesion, viability, and extracellular charge transfer ability of S. oneidensis on the surface of electrodes modified with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), which is a conducting polymer frequently used to enhance the performance of MFCs. PEDOT:PSS-coated glass surface was modified with organic moieties, namely, glucose, sucrose, maltose, cellulose, chitosan, poly(vinyl alcohol), poly-l-lysine, and laminin. The modified surfaces were then analyzed using Fourier-transform infrared spectroscopy, energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, scanning electron microscopy, and fluorescence microscopy, and the results demonstrated an overall improvement in their chemical composition, substantial roughness, and moderate wettability. Biofilm formation was found to be significantly improved on PEDOT:PSS surface coated with glucose, resulting in 54.8 ± 1.2% increase in the amount of biomass. LIVE/DEAD analysis indicated a significantly higher percentage of live bacteria (97.5 ± 1.5%) on the PEDOT:PSS surface coated with glucose when compared to bare PEDOT:PSS (42.1 ± 2.1%). The improved adhesion of S. oneidensis on the glucose-functionalized PEDOT:PSS surface resulted in enhanced charge transfer characteristics, leading to significant decrease in charge transfer resistance at the electrode interface. Our approach shows promise in the further development of efficient renewable energy technology for bioelectricity generation.
{"title":"Surface-Functionalized PEDOT:PSS Interfaces for Improved Adhesion, Viability, and Extracellular Charge Transfer of Shewanella oneidensis MR-1","authors":"Abdullah, Sara Shakibania, Taral Patel, Divine Yufetar Shyntum, Katarzyna Krukiewicz","doi":"10.1021/acssuschemeng.4c05458","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05458","url":null,"abstract":"<i>Shewanella oneidensis</i> MR-1 is an electroactive bacterium commonly employed in the design of microbial fuel cells (MFCs) due to its ability to convert organic matter to electricity. Its applicability is limited by low adhesion to the surface of the electrode, which decreases the efficiency of charge transfer and reduces the available power outputs. In this study, we aimed to improve the adhesion, viability, and extracellular charge transfer ability of <i>S. oneidensis</i> on the surface of electrodes modified with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), which is a conducting polymer frequently used to enhance the performance of MFCs. PEDOT:PSS-coated glass surface was modified with organic moieties, namely, glucose, sucrose, maltose, cellulose, chitosan, poly(vinyl alcohol), poly-<span>l</span>-lysine, and laminin. The modified surfaces were then analyzed using Fourier-transform infrared spectroscopy, energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, scanning electron microscopy, and fluorescence microscopy, and the results demonstrated an overall improvement in their chemical composition, substantial roughness, and moderate wettability. Biofilm formation was found to be significantly improved on PEDOT:PSS surface coated with glucose, resulting in 54.8 ± 1.2% increase in the amount of biomass. LIVE/DEAD analysis indicated a significantly higher percentage of live bacteria (97.5 ± 1.5%) on the PEDOT:PSS surface coated with glucose when compared to bare PEDOT:PSS (42.1 ± 2.1%). The improved adhesion of <i>S. oneidensis</i> on the glucose-functionalized PEDOT:PSS surface resulted in enhanced charge transfer characteristics, leading to significant decrease in charge transfer resistance at the electrode interface. Our approach shows promise in the further development of efficient renewable energy technology for bioelectricity generation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"82 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832660","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 : 2024-12-16DOI: 10.1021/acssuschemeng.4c07021
Dhananjay Dileep, Michael J. Forrester, Jack Bonde, Valentina Camelo Vega, Lauren Burton, Ting-Han Lee, Aleksei Ananin, Baker Kuehl, George A. Kraus, Eric W. Cochran
About 20–34 billion poly(ethylene terephthalate) (PET) bottles from the beverage industry leak into aquatic ecosystems annually, necessitating the development of urgent strategies to treat waterborne plastic pollution. Inspired by the scalability of water disinfection infrastructure and protocols, we present a dual depolymerization approach relying on oxidation, followed by hydrolysis. Incorporating bioderived monounsaturated C18 diacid (C18:1-DA) counits at low dosages (2–5%) in the PET backbone overcomes the diffusional limitations of depolymerizing PET in the solid state by suppressing the glass transition temperature of the copolymer by 20 °C. Cryomilled C18:1-PET powder suspended in an oxidant-loaded alkaline slurry underwent bulk depolymerization to oligomers at 80–100 °C via oxidative scissions at the internally located unsaturations. In contrast, conventional PET undergoes only minor end-chain scission under mild alkaline conditions. These oligomers are suitable for low-energy repolymerization or facile solvolysis to monomers. A permanganate-periodate oxidant couple demonstrated successful oxidation through the bulk of the polymer, which subsequently was hydrolyzed to monomers. This model system serves as a proxy for ozonolysis, followed by mild hydrolysis to reduce the energetics of alkaline hydrolysis. This integrated oxidation–hydrolysis strategy paves the way for the industrial adoption of cleaner, advanced oxidation processes, such as ozonolysis for plastic pretreatment, further enabling commercialized chemical recycling of unsaturation-containing polyesters.
每年约有 200-340 亿个来自饮料行业的聚对苯二甲酸乙二酯（PET）瓶泄漏到水生生态系统中，因此有必要制定紧急战略来处理水生塑料污染。受水消毒基础设施和方案可扩展性的启发，我们提出了一种先氧化后水解的双重解聚方法。在 PET 骨架中加入低剂量（2-5%）的生物源单不饱和 C18 二酸（C18:1-DA）偶联剂，通过将共聚物的玻璃化转变温度降低 20 °C，克服了固态 PET 解聚的扩散限制。悬浮在含氧化剂碱性浆料中的冷冻C18:1-PET粉末在80-100 °C温度下，通过内部不饱和层的氧化裂解，大量解聚成低聚物。相比之下，传统 PET 在温和的碱性条件下仅会发生轻微的端链裂解。这些低聚物适用于低能再聚合或容易溶解为单体。高锰酸盐-碘酸氧化剂偶联物成功地氧化了聚合物的大部分，随后水解为单体。该模型系统可作为臭氧分解的替代物，随后进行温和水解，以降低碱性水解的能耗。这种综合氧化-水解策略为工业上采用更清洁的高级氧化工艺（如用于塑料预处理的臭氧分解）铺平了道路，从而进一步实现了含不饱和聚酯的商业化化学回收。
{"title":"Not Cutting Corners: Bioderived Triggers Driving Oxidative Main Chain Scission of Poly(ethylene terephthalate)","authors":"Dhananjay Dileep, Michael J. Forrester, Jack Bonde, Valentina Camelo Vega, Lauren Burton, Ting-Han Lee, Aleksei Ananin, Baker Kuehl, George A. Kraus, Eric W. Cochran","doi":"10.1021/acssuschemeng.4c07021","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07021","url":null,"abstract":"About 20–34 billion poly(ethylene terephthalate) (PET) bottles from the beverage industry leak into aquatic ecosystems annually, necessitating the development of urgent strategies to treat waterborne plastic pollution. Inspired by the scalability of water disinfection infrastructure and protocols, we present a dual depolymerization approach relying on oxidation, followed by hydrolysis. Incorporating bioderived monounsaturated C18 diacid (C18:1-DA) counits at low dosages (2–5%) in the PET backbone overcomes the diffusional limitations of depolymerizing PET in the solid state by suppressing the glass transition temperature of the copolymer by 20 °C. Cryomilled C18:1-PET powder suspended in an oxidant-loaded alkaline slurry underwent bulk depolymerization to oligomers at 80–100 °C via oxidative scissions at the internally located unsaturations. In contrast, conventional PET undergoes only minor end-chain scission under mild alkaline conditions. These oligomers are suitable for low-energy repolymerization or facile solvolysis to monomers. A permanganate-periodate oxidant couple demonstrated successful oxidation through the bulk of the polymer, which subsequently was hydrolyzed to monomers. This model system serves as a proxy for ozonolysis, followed by mild hydrolysis to reduce the energetics of alkaline hydrolysis. This integrated oxidation–hydrolysis strategy paves the way for the industrial adoption of cleaner, advanced oxidation processes, such as ozonolysis for plastic pretreatment, further enabling commercialized chemical recycling of unsaturation-containing polyesters.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"115 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832724","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}
Lignin, an abundant and complex aromatic biopolymer, holds significant potential for producing value-added chemicals and materials. However, its utilization is limited by its solubility in common organic solvents. In this study, we investigated the solubility of softwood Kraft lignin in benzyl alcohol and compared it to other traditionally studied solvents. Methanol achieved a lignin solubility yield of 59%, while ethanol (18%) and acetone (34%), due to their longer alkyl chains and lower polarity, were less effective in solubilizing larger lignin fragments. Benzyl alcohol, on the other hand, exhibited a complete dissolution of lignin, thereby exceeding by far the capability of the standard solvents. Furthermore, benzyl alcohol resulted in a moderate molecular weight of 3621 g/mol for the lignin fragments and a narrow polydispersity index of 1.54. The complete solubility of lignin in benzyl alcohol suggests significant potential for high yield lignin fractionation and subsequent chemical modifications, which are essential for valorization. Despite the high boiling point of benzyl alcohol, the enhanced solubility could facilitate the production of homogeneous lignin fractions with increased reactive sites, thereby broadening the scope of lignin applications in coatings and industrial materials.
{"title":"Use of Benzyl Alcohol as a Solvent for Kraft Lignin","authors":"Tejasvi Laxminarayan, Søren Kiil, Narayanan Rajagopalan","doi":"10.1021/acssuschemeng.4c07882","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07882","url":null,"abstract":"Lignin, an abundant and complex aromatic biopolymer, holds significant potential for producing value-added chemicals and materials. However, its utilization is limited by its solubility in common organic solvents. In this study, we investigated the solubility of softwood Kraft lignin in benzyl alcohol and compared it to other traditionally studied solvents. Methanol achieved a lignin solubility yield of 59%, while ethanol (18%) and acetone (34%), due to their longer alkyl chains and lower polarity, were less effective in solubilizing larger lignin fragments. Benzyl alcohol, on the other hand, exhibited a complete dissolution of lignin, thereby exceeding by far the capability of the standard solvents. Furthermore, benzyl alcohol resulted in a moderate molecular weight of 3621 g/mol for the lignin fragments and a narrow polydispersity index of 1.54. The complete solubility of lignin in benzyl alcohol suggests significant potential for high yield lignin fractionation and subsequent chemical modifications, which are essential for valorization. Despite the high boiling point of benzyl alcohol, the enhanced solubility could facilitate the production of homogeneous lignin fractions with increased reactive sites, thereby broadening the scope of lignin applications in coatings and industrial materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"77 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832717","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}
Enhanced polysaccharide hydrolysis is essential for converting polysaccharides into mono- and oligosaccharide sugars for use in food, pharmaceutical, and biobased chemical applications. In this study, we developed an efficient continuous-flow hydrolysis process by applying microwaves and sulfonated carbon catalyst (AC-SO3H) using cellobiose as a model sugar substrate. We built a microwave flow reactor equipped with a rectangular waveguide and a solid-state microwave generator capable of applying microwaves to a fixed catalyst bed with spatially separated electric (E-) and magnetic (H-) fields and showed that the microwave flow reaction under the E-field improves the glucose formation rate up to 21.7 mmol/g per hour, which is 35.3 times higher than that achieved in the batch microwave reactor. AC-SO3H showed 16–30 times higher activity than Amberlyst 70 because of the higher dielectric loss tangent (tan δ) value of AC-SO3H (0.187) than Amberlyst 70 (0.040). H-field heating of AC-SO3H also improved the glucose formation rate by 1.2–1.6 times. Notably, the H-field reduced the microwave power to 45% of that of the E-field. Therefore, a microwave H-field flow reactor equipped with an AC-SO3H catalyst greatly improves both the glucose production rate and energy efficiency of cellobiose hydrolysis.
{"title":"Efficient Cellobiose Hydrolysis over a Sulfonated Carbon Catalyst in a Spatially Separated Microwave Electric- and Magnetic-Field Flow Reactor","authors":"Shuntaro Tsubaki, Kazuaki Senda, Ayumu Onda, Satoshi Fujii","doi":"10.1021/acssuschemeng.4c07690","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07690","url":null,"abstract":"Enhanced polysaccharide hydrolysis is essential for converting polysaccharides into mono- and oligosaccharide sugars for use in food, pharmaceutical, and biobased chemical applications. In this study, we developed an efficient continuous-flow hydrolysis process by applying microwaves and sulfonated carbon catalyst (AC-SO<sub>3</sub>H) using cellobiose as a model sugar substrate. We built a microwave flow reactor equipped with a rectangular waveguide and a solid-state microwave generator capable of applying microwaves to a fixed catalyst bed with spatially separated electric (<i>E</i>-) and magnetic (<i>H</i>-) fields and showed that the microwave flow reaction under the <i>E</i>-field improves the glucose formation rate up to 21.7 mmol/g per hour, which is 35.3 times higher than that achieved in the batch microwave reactor. AC-SO<sub>3</sub>H showed 16–30 times higher activity than Amberlyst 70 because of the higher dielectric loss tangent (tan δ) value of AC-SO<sub>3</sub>H (0.187) than Amberlyst 70 (0.040). <i>H</i>-field heating of AC-SO<sub>3</sub>H also improved the glucose formation rate by 1.2–1.6 times. Notably, the <i>H</i>-field reduced the microwave power to 45% of that of the <i>E</i>-field. Therefore, a microwave <i>H</i>-field flow reactor equipped with an AC-SO<sub>3</sub>H catalyst greatly improves both the glucose production rate and energy efficiency of cellobiose hydrolysis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832716","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 : 2024-12-16DOI: 10.1021/acssuschemeng.4c07052
Chenglong Li, Qun Wang, Qihang Tan, Lei Yang, Long Liu, Tianzeng Huang, Michal Szostak, Tieqiao Chen
Due to the nN-to-π*C═O conjugation, the direct functionalization of unactivated amides via C−N activation is a longstanding challenge in functional group interconversion involving ubiquitous amide linkages. Herein, we report highly chemoselective esterification of unactivated tertiary amides with various equivalent oxygen nucleophiles, including both aliphatic alcohols and weakly nucleophilic phenols, for the first time. In this reaction, amide C−N bonds are electrophilically activated through cooperative acid/iodide catalysis via the selective formation of a highly reactive acyl iodide species. This powerful strategy enables the use of a stoichiometric quantity of O−H nucleophiles and provides the first general method for converting unactivated N,N-dialkyl amides into the corresponding esters with exquisite chemoselectivity. An exceptionally wide substrate scope of both amides and oxygen nucleophiles is demonstrated with high functional group tolerance, including the late-stage modification of some drugs’ amide derivatives and bioactive O−H nucleophiles (>100 examples). We anticipate that this powerful esterification of amides will find wide application in synthetic organic chemistry.
{"title":"Acid/Iodide Cooperative Catalysis for Highly Chemoselective Esterification of Unactivated Tertiary Amides via Electrophilic N−C(O) Activation","authors":"Chenglong Li, Qun Wang, Qihang Tan, Lei Yang, Long Liu, Tianzeng Huang, Michal Szostak, Tieqiao Chen","doi":"10.1021/acssuschemeng.4c07052","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07052","url":null,"abstract":"Due to the n<sub>N</sub>-to-π*<sub>C═O</sub> conjugation, the direct functionalization of unactivated amides via C−N activation is a longstanding challenge in functional group interconversion involving ubiquitous amide linkages. Herein, we report highly chemoselective esterification of unactivated tertiary amides with various equivalent oxygen nucleophiles, including both aliphatic alcohols and weakly nucleophilic phenols, for the first time. In this reaction, amide C−N bonds are electrophilically activated through cooperative acid/iodide catalysis via the selective formation of a highly reactive acyl iodide species. This powerful strategy enables the use of a stoichiometric quantity of O−H nucleophiles and provides the first general method for converting unactivated <i>N,N</i>-dialkyl amides into the corresponding esters with exquisite chemoselectivity. An exceptionally wide substrate scope of both amides and oxygen nucleophiles is demonstrated with high functional group tolerance, including the late-stage modification of some drugs’ amide derivatives and bioactive O−H nucleophiles (>100 examples). We anticipate that this powerful esterification of amides will find wide application in synthetic organic chemistry.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832664","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 : 2024-12-16DOI: 10.1021/acssuschemeng.4c08299
Jia’nan Zhang, Zizhen Liu, Yihan Wang, Bo Yu
l-Homoserine is proven to be a promising precursor for the synthesis of l-phosphinothricin, which is a broad-spectrum herbicide with low toxicity. To enhance the sustainability of the process, the utilization of nonfood carbon sources for l-homoserine production is highly sought-after. Acetate, which can be captured from C1 gases, has the potential to become the most abundant feedstock for biomanufacturing. In this study, we systematically engineered the Escherichia coli strain to generate l-homoserine from acetate. The production of l-homoserine from acetate was initially achieved by deleting branch pathways, activating the glyoxylate shunt, and enhancing the synthetic pathway. The strain’s tolerance and acetate assimilation capabilities were strengthened through adaptive laboratory evolution. Reducing the flux toward gluconeogenesis further facilitated the production of l-homoserine. Finally, the engineered strain produced 15.96 g/L l-homoserine solely from CO2-derived acetate and formate in a 5 L fermentor via a fed-batch process. This study provides insights into the development of a low-carbon bioeconomy for the herbicide industry.
{"title":"Sustainable Production of l-Homoserine Solely from CO2-Derived Acetate and Formate by Engineered E. coli Strain","authors":"Jia’nan Zhang, Zizhen Liu, Yihan Wang, Bo Yu","doi":"10.1021/acssuschemeng.4c08299","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08299","url":null,"abstract":"<span>l</span>-Homoserine is proven to be a promising precursor for the synthesis of <span>l</span>-phosphinothricin, which is a broad-spectrum herbicide with low toxicity. To enhance the sustainability of the process, the utilization of nonfood carbon sources for <span>l</span>-homoserine production is highly sought-after. Acetate, which can be captured from C1 gases, has the potential to become the most abundant feedstock for biomanufacturing. In this study, we systematically engineered the <i>Escherichia coli</i> strain to generate <span>l</span>-homoserine from acetate. The production of <span>l</span>-homoserine from acetate was initially achieved by deleting branch pathways, activating the glyoxylate shunt, and enhancing the synthetic pathway. The strain’s tolerance and acetate assimilation capabilities were strengthened through adaptive laboratory evolution. Reducing the flux toward gluconeogenesis further facilitated the production of <span>l</span>-homoserine. Finally, the engineered strain produced 15.96 g/L <span>l</span>-homoserine solely from CO<sub>2</sub>-derived acetate and formate in a 5 L fermentor via a fed-batch process. This study provides insights into the development of a low-carbon bioeconomy for the herbicide industry.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"46 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832719","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 : 2024-12-13DOI: 10.1021/acssuschemeng.4c08547
Boning Su, Mingchuan Yang, Bin Gao, Xiangjie Zhao, Ziyao Li, Shugang Zhang, Dongdong Cheng, Tianlin Shen, Yuanyuan Yao, Yuechao Yang
The maturation of biobased polymer synthesis process has led to the rapid adoption of biobased controlled-release fertilizers (BCRFs). Despite this progress, the loose structure, low cross-linking density, and poor water repellency of current biobased coatings result in short controlled-release periods, which do not meet the long-term nutrient demands of crops throughout their reproductive phases. Moreover, existing modifications to address these issues often involve the addition of external additives, which can increase biotoxicity and cost. In this study, castor oil-based hyperbranched polyol (COHBPs) was synthesized from castor oil (CO) using a “one-pot method.” We report the development of high cross-linking density biobased hyperbranched polyurethane (COHBPPFs) as a coating for BCRFs. Gel content and SEM analysis demonstrated that COHBPPFs exhibited a high degree of cross-linking. Mechanical testing using an electronic universal testing machine, along with AFM results, highlighted the superior mechanical properties of COHBPPFs compared to traditional coatings. COHBPPFs significantly enhanced controlled release performance, with a 3% coating content providing nearly 50 days of controlled release, a marked improvement over conventional coatings. The controlled release mechanism of COHBPPFs was elucidated by modeling the cross-linking process of COHBPs with PAPI. This study offers a comprehensive examination of CRF coatings from multiple perspectives and provides valuable insights into the development of high cross-link density, environmentally friendly, and renewable biobased CRFs.
{"title":"Enhancing Longevity and Mechanisms of Controlled-Release Fertilizers Through High Cross-Link Density Hyperbranched Bio-Based Polyurethane Coatings","authors":"Boning Su, Mingchuan Yang, Bin Gao, Xiangjie Zhao, Ziyao Li, Shugang Zhang, Dongdong Cheng, Tianlin Shen, Yuanyuan Yao, Yuechao Yang","doi":"10.1021/acssuschemeng.4c08547","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08547","url":null,"abstract":"The maturation of biobased polymer synthesis process has led to the rapid adoption of biobased controlled-release fertilizers (BCRFs). Despite this progress, the loose structure, low cross-linking density, and poor water repellency of current biobased coatings result in short controlled-release periods, which do not meet the long-term nutrient demands of crops throughout their reproductive phases. Moreover, existing modifications to address these issues often involve the addition of external additives, which can increase biotoxicity and cost. In this study, castor oil-based hyperbranched polyol (COHBPs) was synthesized from castor oil (CO) using a “one-pot method.” We report the development of high cross-linking density biobased hyperbranched polyurethane (COHBPPFs) as a coating for BCRFs. Gel content and SEM analysis demonstrated that COHBPPFs exhibited a high degree of cross-linking. Mechanical testing using an electronic universal testing machine, along with AFM results, highlighted the superior mechanical properties of COHBPPFs compared to traditional coatings. COHBPPFs significantly enhanced controlled release performance, with a 3% coating content providing nearly 50 days of controlled release, a marked improvement over conventional coatings. The controlled release mechanism of COHBPPFs was elucidated by modeling the cross-linking process of COHBPs with PAPI. This study offers a comprehensive examination of CRF coatings from multiple perspectives and provides valuable insights into the development of high cross-link density, environmentally friendly, and renewable biobased CRFs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820748","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 : 2024-12-13DOI: 10.1021/acssuschemeng.4c07423
Shiyi Qin, Surajudeen Omolabake, Aminata Diaby, Jianping Li, Leonardo D. González, Christopher M. Holland, Victor M. Zavala, Shannon S. Stahl, Reid C. Van Lehn
Liquid–liquid extraction (LLE) is a widely used technique for the separation and purification of liquid-phase products with applications in various industries, including pharmaceuticals, petrochemicals, and renewable chemistry. A critical step in the design of an LLE process is the selection of appropriate solvents. This study presents a new methodology for identifying solvent mixtures for bioproduct separation using Bayesian experimental design (BED). Motivated by the need for environmentally friendly and effective separation methods, we address the challenge of selecting solvent systems that balance separation efficiency, selectivity, and environmental impact while also tackling the difficulty of separating multiple bioproducts using complex solvent systems. Our approach specifically seeks to predict product partition coefficients (log10Kp values) as thermodynamic parameters underlying solvent selection. The iterative approach integrates Bayesian optimization with experimental measurements to guide solvent selection and leverages COSMO-RS simulations to enhance high-throughput experimentation. Using the design of solvent systems for the separation of lignin-derived aromatic products via centrifugal partition chromatography (CPC) as a case study, we show that within seven iterations/cycles of the methodology, we can identify new mixtures of green solvents that align with CPC design principles. These results demonstrate the efficacy of the BED framework in optimizing green solvent systems for complex separations, highlighting the potential of this method to advance the field of green chemistry and contribute to the development of sustainable industrial processes.
{"title":"Identifying Green Solvent Mixtures for Bioproduct Separation Using Bayesian Experimental Design","authors":"Shiyi Qin, Surajudeen Omolabake, Aminata Diaby, Jianping Li, Leonardo D. González, Christopher M. Holland, Victor M. Zavala, Shannon S. Stahl, Reid C. Van Lehn","doi":"10.1021/acssuschemeng.4c07423","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07423","url":null,"abstract":"Liquid–liquid extraction (LLE) is a widely used technique for the separation and purification of liquid-phase products with applications in various industries, including pharmaceuticals, petrochemicals, and renewable chemistry. A critical step in the design of an LLE process is the selection of appropriate solvents. This study presents a new methodology for identifying solvent mixtures for bioproduct separation using Bayesian experimental design (BED). Motivated by the need for environmentally friendly and effective separation methods, we address the challenge of selecting solvent systems that balance separation efficiency, selectivity, and environmental impact while also tackling the difficulty of separating multiple bioproducts using complex solvent systems. Our approach specifically seeks to predict product partition coefficients (log<sub>10</sub> <i>K</i><sub>p</sub> values) as thermodynamic parameters underlying solvent selection. The iterative approach integrates Bayesian optimization with experimental measurements to guide solvent selection and leverages COSMO-RS simulations to enhance high-throughput experimentation. Using the design of solvent systems for the separation of lignin-derived aromatic products via centrifugal partition chromatography (CPC) as a case study, we show that within seven iterations/cycles of the methodology, we can identify new mixtures of green solvents that align with CPC design principles. These results demonstrate the efficacy of the BED framework in optimizing green solvent systems for complex separations, highlighting the potential of this method to advance the field of green chemistry and contribute to the development of sustainable industrial processes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"142 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816459","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：