Pub Date : 2024-12-20DOI: 10.1021/acssuschemeng.4c04185
Jia Wang, Wen-Cui Li, Dan-Hui Sun, Lei He, Bai-Chuan Zhou, An-Hui Lu
The catalytic upgrading of renewable ethanol to C4–10 alcohols via C–C coupling offers a green and negative-carbon-emission pathway toward value-added compounds. The manipulation of catalysts’ surface basic and acidic properties is the key to achieve high-selectivity C4–10 alcohols. In this study, we present a solvent-free mechanochemical approach for the synthesis of hydroxyapatite (HAP) catalysts with enhanced basicity. The selectivity for a total C4–10 alcohols reaches 97.8% with a yield of 53.9% at 325 °C and 0.1 MPa, surpassing previously reported catalysts in the literature. The mechanochemically synthesized HAP catalysts extend along the c-axis and expose the (002) crystal plane with enriched strong basic [Ca–O–P] sites. CO2-TPD and XPS analyses demonstrated that the hydrogen bonds between the oxygen atoms of adjoining phosphate groups enhance the basic property of the catalyst surfaces. The kinetic measurements have demonstrated that the abundance of strong basic sites facilitates the adsorption of ethanol molecules and accelerates the rate of C–C coupling reactions, which is responsible for a high yield of C4–10 alcohols. This work offers a sustainable approach for synthesizing such alcohols and stimulates the advancement of environmentally friendly catalysts.
{"title":"High-Selective Upgrading of Ethanol to C4–10 Alcohols over Hydroxyapatite Catalyst with Superior Basicity","authors":"Jia Wang, Wen-Cui Li, Dan-Hui Sun, Lei He, Bai-Chuan Zhou, An-Hui Lu","doi":"10.1021/acssuschemeng.4c04185","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04185","url":null,"abstract":"The catalytic upgrading of renewable ethanol to C<sub>4–10</sub> alcohols via C–C coupling offers a green and negative-carbon-emission pathway toward value-added compounds. The manipulation of catalysts’ surface basic and acidic properties is the key to achieve high-selectivity C<sub>4–10</sub> alcohols. In this study, we present a solvent-free mechanochemical approach for the synthesis of hydroxyapatite (HAP) catalysts with enhanced basicity. The selectivity for a total C<sub>4–10</sub> alcohols reaches 97.8% with a yield of 53.9% at 325 °C and 0.1 MPa, surpassing previously reported catalysts in the literature. The mechanochemically synthesized HAP catalysts extend along the <i>c</i>-axis and expose the (002) crystal plane with enriched strong basic [Ca–O–P] sites. CO<sub>2</sub>-TPD and XPS analyses demonstrated that the hydrogen bonds between the oxygen atoms of adjoining phosphate groups enhance the basic property of the catalyst surfaces. The kinetic measurements have demonstrated that the abundance of strong basic sites facilitates the adsorption of ethanol molecules and accelerates the rate of C–C coupling reactions, which is responsible for a high yield of C<sub>4–10</sub> alcohols. This work offers a sustainable approach for synthesizing such alcohols and stimulates the advancement of environmentally friendly catalysts.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857922","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 : 2024-12-19DOI: 10.1021/acssuschemeng.4c07302
Wei Luo, Jie Shi, Tiesen Li, Tinghai Wang, Jiangyong Liu, Qingyan Cui, Yisheng Tan, Yuanyuan Yue, Xiaojun Bao
The catalytic dehydration of glycerol to acrolein offers a sustainable route for efficiently utilizing low-cost and renewable bioglycerol. This work deeply explores glycerol dehydration to acrolein over ZSM-5 zeolite catalysts with various pore structures and aluminum distributions. The results reveal that glycerol conversion is enhanced through the construction of a mesoporous structure and the increase in Brønsted acid sites of the catalysts, but acrolein selectivity is not directly related to these factors. Further characterizations, density functional theory calculation, kinetic study, and reaction mechanism analysis demonstrate that the richest Alsingle sites in the zeolite framework and the least Alpair sites in the straight and sinusoidal channels can prevent the generated acrolein from adsorbing on adjacent Al sites. This allows acrolein to immediately escape from the catalyst surface, reducing side reactions and enhancing its selectivity. Therefore, the synergistic between the mesoporous structure and more Alsingle sites in the ZSM-5 zeolite framework promotes acrolein yield. Additionally, a descriptor φ, reflecting the amount of Alsingle sites and the external specific surface area of the ZSM-5 zeolite, is first proposed to more clearly elucidate the structure–performance relationship. This study provides a new perspective for understanding the mechanism of catalytic dehydration of glycerol to acrolein, guiding the development of highly efficient catalysts. It is significant for the sustainable development of the biodiesel and acrolein production industry.
{"title":"Catalytic Dehydration of Glycerol to Acrolein over ZSM-5 Zeolites: Synergistic Effect of Pore Structure and Aluminum Distribution","authors":"Wei Luo, Jie Shi, Tiesen Li, Tinghai Wang, Jiangyong Liu, Qingyan Cui, Yisheng Tan, Yuanyuan Yue, Xiaojun Bao","doi":"10.1021/acssuschemeng.4c07302","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07302","url":null,"abstract":"The catalytic dehydration of glycerol to acrolein offers a sustainable route for efficiently utilizing low-cost and renewable bioglycerol. This work deeply explores glycerol dehydration to acrolein over ZSM-5 zeolite catalysts with various pore structures and aluminum distributions. The results reveal that glycerol conversion is enhanced through the construction of a mesoporous structure and the increase in Brønsted acid sites of the catalysts, but acrolein selectivity is not directly related to these factors. Further characterizations, density functional theory calculation, kinetic study, and reaction mechanism analysis demonstrate that the richest Al<sub>single</sub> sites in the zeolite framework and the least Al<sub>pair</sub> sites in the straight and sinusoidal channels can prevent the generated acrolein from adsorbing on adjacent Al sites. This allows acrolein to immediately escape from the catalyst surface, reducing side reactions and enhancing its selectivity. Therefore, the synergistic between the mesoporous structure and more Al<sub>single</sub> sites in the ZSM-5 zeolite framework promotes acrolein yield. Additionally, a descriptor φ, reflecting the amount of Al<sub>single</sub> sites and the external specific surface area of the ZSM-5 zeolite, is first proposed to more clearly elucidate the structure–performance relationship. This study provides a new perspective for understanding the mechanism of catalytic dehydration of glycerol to acrolein, guiding the development of highly efficient catalysts. It is significant for the sustainable development of the biodiesel and acrolein production industry.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"99 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857925","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 : 2024-12-19DOI: 10.1021/acssuschemeng.4c05508
Sara Fulignati, Anna Maria Raspolli Galletti, Francesca Barsotti, Virginia Menicagli, Elena Balestri, Claudio Lardicci, Marco Mattonai, Federica Nardella, Claudia Antonetti
This work proposes the integrated exploitation of fibrous balls of seagrass Posidonia oceanica (PO), which annually accumulate along the sandy Mediterranean beaches, causing significant management and economic problems. Preliminarily, the organic extractives of PO balls were removed by ethanol, and their characterization highlighted the presence of biologically active molecules. The successive alkaline pretreatment allowed the fractionation of the biomass, leading to a solid enriched in polysaccharides and a “black liquor” containing the extracted lignin. The butanolysis of the solid enriched in polysaccharides provided a yield of up to 52.3 mol % of butyl levulinate, a strategic intermediate, and valuable bioblendstock for diesel. Finally, pure acid-insoluble lignin and acid-soluble lignin fractions were recovered from the “black liquor”. These were deeply characterized and proposed as UV-blocker and antioxidant agents.
{"title":"Sustainable Exploitation of Posidonia oceanica Balls through an Integrated Biorefinery Approach","authors":"Sara Fulignati, Anna Maria Raspolli Galletti, Francesca Barsotti, Virginia Menicagli, Elena Balestri, Claudio Lardicci, Marco Mattonai, Federica Nardella, Claudia Antonetti","doi":"10.1021/acssuschemeng.4c05508","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05508","url":null,"abstract":"This work proposes the integrated exploitation of fibrous balls of seagrass <i>Posidonia oceanica</i> (PO), which annually accumulate along the sandy Mediterranean beaches, causing significant management and economic problems. Preliminarily, the organic extractives of PO balls were removed by ethanol, and their characterization highlighted the presence of biologically active molecules. The successive alkaline pretreatment allowed the fractionation of the biomass, leading to a solid enriched in polysaccharides and a “black liquor” containing the extracted lignin. The butanolysis of the solid enriched in polysaccharides provided a yield of up to 52.3 mol % of butyl levulinate, a strategic intermediate, and valuable bioblendstock for diesel. Finally, pure acid-insoluble lignin and acid-soluble lignin fractions were recovered from the “black liquor”. These were deeply characterized and proposed as UV-blocker and antioxidant agents.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857926","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}
In this research, corn stover was pretreated by the white-rot fungus Trametes versicolor via solid-state fermentation. Nine primary factors influencing solid-state fermentation were examined through single-factor optimization. The average laccase-specific activity rose from 68.184 to 83.098 U/g, resulting in a 21.87% improvement in fermentation efficiency. Post-solid-state fermentation, steam explosion was employed to remove hemicellulose, aiding subsequent enzymatic degradation. The degradation ratio of lignin and other components reached 45.90% after the biological pretreatment and steam explosion. At the same time, the cellulose content in the resulting solid substrate increased from 38.03 to 64.71%. Subsequently, five heterologous thermostable enzymes were combined with cellulase to process the cellulose in a “one-pot method.” After optimization of reaction conditions, this in vitro synthetic multienzyme catalytic system was capable of producing 4.596 g of inositol per 10 g of pretreated corn stalks. Based on the degradation products of cellulase, the final yield of inositol in the multienzyme cascades reached 89.42% of the theoretical yield. This study demonstrated the feasibility of converting natural raw materials to value-added chemicals using biological methods.
{"title":"Biomanufacturing of Inositol from Corn Stover with Biological Pretreatment by an In Vitro Synthetic Biology Platform","authors":"Yingjie Pan, Yifan Liu, Tieu Long Phan, Jialun Gao, Yong Wang, Hao Fang","doi":"10.1021/acssuschemeng.4c08006","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08006","url":null,"abstract":"In this research, corn stover was pretreated by the white-rot fungus <i>Trametes versicolor</i> via solid-state fermentation. Nine primary factors influencing solid-state fermentation were examined through single-factor optimization. The average laccase-specific activity rose from 68.184 to 83.098 U/g, resulting in a 21.87% improvement in fermentation efficiency. Post-solid-state fermentation, steam explosion was employed to remove hemicellulose, aiding subsequent enzymatic degradation. The degradation ratio of lignin and other components reached 45.90% after the biological pretreatment and steam explosion. At the same time, the cellulose content in the resulting solid substrate increased from 38.03 to 64.71%. Subsequently, five heterologous thermostable enzymes were combined with cellulase to process the cellulose in a “one-pot method.” After optimization of reaction conditions, this in vitro synthetic multienzyme catalytic system was capable of producing 4.596 g of inositol per 10 g of pretreated corn stalks. Based on the degradation products of cellulase, the final yield of inositol in the multienzyme cascades reached 89.42% of the theoretical yield. This study demonstrated the feasibility of converting natural raw materials to value-added chemicals using biological methods.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857927","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 : 2024-12-19DOI: 10.1021/acssuschemeng.4c08020
Daniela Meroni, Carolina Cionti, Giovanni Vavassori, Daniela Maggioni, Giuseppe Cappelletti
In situ-functionalized Pickering emulsions can exhibit phase inversion by changing the concentration of surface modifiers. Here, we demonstrate that these systems are far more versatile as multiple stimuli can be harnessed to achieve their phase inversion. Oil-in-water Pickering emulsions were prepared using food-grade vegetable oil and stabilized solely by in situ-functionalized ZnO particles. ZnO was selected for its semiconductor and amphoteric properties, which enable the controlled switching/destabilization activated by multiple stimuli: acidification by mineral and organic acids, UV and sunlight irradiation, addition of multivalent cations and CO2 bubbling. Depending on the stimulus, the switching kinetics and reversibility can be tailored. Switching by acidification, light irradiation or CO2 bubbling is fully reversible upon either pH increase, N2 bubbling or storage in the dark. Even after consecutive cycles, stable oil-in-water Pickering emulsions could be reobtained. Irreversible destabilization can instead be triggered by excess addition of acids and multivalent cations. The switching kinetics can be modulated achieving either an on–off behavior or a controlled destabilization over several hours. The oil phase of the emulsion can be loaded with active substances, such as volatile and unstable essential oils. Emulsions containing cinnamaldehyde (up to 1500 ppm) were prepared and destabilized after accelerated aging: the molecule was stored and released in the aqueous phase without undergoing any degradation, with concentrations in a range suitable to avoid proliferation of bacteria and fungi. Up to four consecutive release cycles were successfully conducted by two different procedures, proving the system’s applicability as a continuous source of the active molecule.
{"title":"Multistimuli Responsive ZnO-Stabilized Pickering Emulsions for the Controlled Release of Essential Oils","authors":"Daniela Meroni, Carolina Cionti, Giovanni Vavassori, Daniela Maggioni, Giuseppe Cappelletti","doi":"10.1021/acssuschemeng.4c08020","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08020","url":null,"abstract":"In situ-functionalized Pickering emulsions can exhibit phase inversion by changing the concentration of surface modifiers. Here, we demonstrate that these systems are far more versatile as multiple stimuli can be harnessed to achieve their phase inversion. Oil-in-water Pickering emulsions were prepared using food-grade vegetable oil and stabilized solely by in situ-functionalized ZnO particles. ZnO was selected for its semiconductor and amphoteric properties, which enable the controlled switching/destabilization activated by multiple stimuli: acidification by mineral and organic acids, UV and sunlight irradiation, addition of multivalent cations and CO<sub>2</sub> bubbling. Depending on the stimulus, the switching kinetics and reversibility can be tailored. Switching by acidification, light irradiation or CO<sub>2</sub> bubbling is fully reversible upon either pH increase, N<sub>2</sub> bubbling or storage in the dark. Even after consecutive cycles, stable oil-in-water Pickering emulsions could be reobtained. Irreversible destabilization can instead be triggered by excess addition of acids and multivalent cations. The switching kinetics can be modulated achieving either an on–off behavior or a controlled destabilization over several hours. The oil phase of the emulsion can be loaded with active substances, such as volatile and unstable essential oils. Emulsions containing cinnamaldehyde (up to 1500 ppm) were prepared and destabilized after accelerated aging: the molecule was stored and released in the aqueous phase without undergoing any degradation, with concentrations in a range suitable to avoid proliferation of bacteria and fungi. Up to four consecutive release cycles were successfully conducted by two different procedures, proving the system’s applicability as a continuous source of the active molecule.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857558","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 : 2024-12-19DOI: 10.1021/acssuschemeng.4c07026
Jun Wu, Liqian Liu, Xinyue Yan, Tingting Wang, Gang Pan, Jiahao Bai, Yong Li
Catalytic hydrodeoxygenation (HDO) of bio-oil is an effective and challenging route to the efficient utilization of biomass with rich oxygen-containing groups. Herein, highly dispersed Pd nanoparticles (NPs) anchored on a N-doped hollow carbon sphere (NHCS) were constructed to effectively catalyze the chemoselective HDO of bio-oil-derived vanillin. The optimized Pd/NHCS-900 catalyst presented a high 99% conversion and 98% selectivity to 2-methoxy-4-methylphenol (MMP) within 45 min under very mild conditions of 50 °C and 1 atm H2. The incorporated N species in the NHCS support and its hierarchical porous structure facilitate the dispersion and stabilization of Pd NPs, resulting in the formation of highly dispersed Pd NPs with excellent structure stability. Moreover, the presence of a strong electronic metal–support interaction between N and highly dispersed Pd NPs produced the surface electron-rich active Pd NPs, which could enhance the adsorption and activation of reactants, thereby exhibiting high intrinsic catalytic activity with a large turnover frequency (TOF) of 1700.3 h–1. Kinetic study and density functional theory (DFT) calculations demonstrated the HDO reaction pathway and the corresponding reaction mechanism. These findings pave the way for the development of efficient and stable metal catalysts for sustainable biomass conversion.
{"title":"Highly Dispersed Pd Nanoparticles Immobilized on N-Doped Hollow Carbon Spheres for Efficient Catalytic Hydrodeoxygenation of Biomass-Derived Vanillin under Atmospheric Conditions","authors":"Jun Wu, Liqian Liu, Xinyue Yan, Tingting Wang, Gang Pan, Jiahao Bai, Yong Li","doi":"10.1021/acssuschemeng.4c07026","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07026","url":null,"abstract":"Catalytic hydrodeoxygenation (HDO) of bio-oil is an effective and challenging route to the efficient utilization of biomass with rich oxygen-containing groups. Herein, highly dispersed Pd nanoparticles (NPs) anchored on a N-doped hollow carbon sphere (NHCS) were constructed to effectively catalyze the chemoselective HDO of bio-oil-derived vanillin. The optimized Pd/NHCS-900 catalyst presented a high 99% conversion and 98% selectivity to 2-methoxy-4-methylphenol (MMP) within 45 min under very mild conditions of 50 °C and 1 atm H<sub>2</sub>. The incorporated N species in the NHCS support and its hierarchical porous structure facilitate the dispersion and stabilization of Pd NPs, resulting in the formation of highly dispersed Pd NPs with excellent structure stability. Moreover, the presence of a strong electronic metal–support interaction between N and highly dispersed Pd NPs produced the surface electron-rich active Pd NPs, which could enhance the adsorption and activation of reactants, thereby exhibiting high intrinsic catalytic activity with a large turnover frequency (TOF) of 1700.3 h<sup>–1</sup>. Kinetic study and density functional theory (DFT) calculations demonstrated the HDO reaction pathway and the corresponding reaction mechanism. These findings pave the way for the development of efficient and stable metal catalysts for sustainable biomass conversion.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857928","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 : 2024-12-19DOI: 10.1021/acssuschemeng.4c07624
Yuehong Zhang, Qinyang Lei, Shutong Zhang, Langlang Dai, Bin Lyu, Leipeng Liu
The development of low-carbon and environmentally friendly unsaturated polyester thermosets has attracted widespread attention. In this work, methacrylated castor oil (MCO) and methacrylated isosorbide (MI) were prepared using renewable castor oil and isosorbide by a simple and mild method. Subsequently, a variety of sustainable unsaturated polyester materials (MCO-MI) were prepared by curing MCO resin with the reactive diluent MI in different ratios via free radical polymerization. The chemical structure, viscosity, biobased carbon content, and LD50 of MCO and MI were evaluated, and the mechanical properties, thermo-mechanical properties, solvent resistance, and life cycle assessment (LCA) of the cured MCO-MI thermosets were investigated. The results showed that MCO and MI exhibited low viscosity (746 and 4 mPa s), chemical toxicity, and high biobased carbon content (85.9 and 76.9%). When the mass ratio of MCO to MI was 40:60, the resulting MCO-MI thermosets had the optimum thermo-mechanical property with a Tg of 170.2 °C and a tensile strength of 35.6 MPa. In addition, the LCA results demonstrated that the MCO-MI thermosets had striking environmental benefits over traditional petroleum-based unsaturated polyester materials containing styrene. This work provides insight into the preparation of environmentally friendly and high-performance unsaturated polyester materials employing biobased building blocks.
低碳环保型不饱和聚酯热固性塑料的开发已引起广泛关注。本研究采用简单温和的方法，利用可再生蓖麻油和异山梨醇制备了甲基丙烯酸化蓖麻油（MCO）和甲基丙烯酸化异山梨醇（MI）。随后，通过自由基聚合将 MCO 树脂与活性稀释剂 MI 以不同比例固化，制备了多种可持续不饱和聚酯材料（MCO-MI）。评估了 MCO 和 MI 的化学结构、粘度、生物基碳含量和 LD50，并研究了固化 MCO-MI 热固性材料的机械性能、热机械性能、耐溶剂性和生命周期评估（LCA）。结果表明，MCO 和 MI 具有低粘度（746 mPa s 和 4 mPa s）、化学毒性和高生物基碳含量（85.9% 和 76.9%）。当 MCO 与 MI 的质量比为 40:60 时，生成的 MCO-MI 热固性塑料具有最佳的热机械性能，Tg 为 170.2 ℃，拉伸强度为 35.6 MPa。此外，生命周期评估结果表明，与含有苯乙烯的传统石油基不饱和聚酯材料相比，MCO-MI 热固性塑料具有显著的环境效益。这项研究为利用生物基建筑模块制备环保型高性能不饱和聚酯材料提供了深入的见解。
{"title":"Biobased Unsaturated Polyester Thermosets from Castor Oil and Isosorbide with Life Cycle Assessment","authors":"Yuehong Zhang, Qinyang Lei, Shutong Zhang, Langlang Dai, Bin Lyu, Leipeng Liu","doi":"10.1021/acssuschemeng.4c07624","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07624","url":null,"abstract":"The development of low-carbon and environmentally friendly unsaturated polyester thermosets has attracted widespread attention. In this work, methacrylated castor oil (MCO) and methacrylated isosorbide (MI) were prepared using renewable castor oil and isosorbide by a simple and mild method. Subsequently, a variety of sustainable unsaturated polyester materials (MCO-MI) were prepared by curing MCO resin with the reactive diluent MI in different ratios via free radical polymerization. The chemical structure, viscosity, biobased carbon content, and LD<sub>50</sub> of MCO and MI were evaluated, and the mechanical properties, thermo-mechanical properties, solvent resistance, and life cycle assessment (LCA) of the cured MCO-MI thermosets were investigated. The results showed that MCO and MI exhibited low viscosity (746 and 4 mPa s), chemical toxicity, and high biobased carbon content (85.9 and 76.9%). When the mass ratio of MCO to MI was 40:60, the resulting MCO-MI thermosets had the optimum thermo-mechanical property with a <i>T</i><sub>g</sub> of 170.2 °C and a tensile strength of 35.6 MPa. In addition, the LCA results demonstrated that the MCO-MI thermosets had striking environmental benefits over traditional petroleum-based unsaturated polyester materials containing styrene. This work provides insight into the preparation of environmentally friendly and high-performance unsaturated polyester materials employing biobased building blocks.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849268","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 : 2024-12-17DOI: 10.1021/acssuschemeng.4c08612
Madison J. Wong, Kaitlyn M. Freiberg, Trevor Reynafarje Jones, Kylee B. Dismuke Rodriguez, Alex B. Wood, Bruce H. Lipshutz
New plug-flow opportunities for carrying out SNAr reactions are disclosed using water mixed with the green and separable/recyclable cosolvent 2-MeTHF. This approach enables C–O, C–N, and C–S bond formations. Several features characteristic of this sustainable technology are highlighted, such as recycling of the aqueous reaction medium, applications to several intermediates en route to numerous active pharmaceutical ingredients, and a new “flow-to-batch-to-flow” sequence of reactions demonstrating the possibilities for both time and pot economies to be realized.
{"title":"SNAr Reactions Using Continuous Plug Flow...in Aqueous Biphasic Media","authors":"Madison J. Wong, Kaitlyn M. Freiberg, Trevor Reynafarje Jones, Kylee B. Dismuke Rodriguez, Alex B. Wood, Bruce H. Lipshutz","doi":"10.1021/acssuschemeng.4c08612","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08612","url":null,"abstract":"New plug-flow opportunities for carrying out S<sub>N</sub>Ar reactions are disclosed using water mixed with the green and separable/recyclable cosolvent 2-MeTHF. This approach enables C–O, C–N, and C–S bond formations. Several features characteristic of this sustainable technology are highlighted, such as recycling of the aqueous reaction medium, applications to several intermediates en route to numerous active pharmaceutical ingredients, and a new “flow-to-batch-to-flow” sequence of reactions demonstrating the possibilities for both time and pot economies to be realized.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832659","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.4c07993
Yan Huang, Zhangpeng Li, Yaochen Wang, Qiulong Gao, Kaiming Hou, Shuwen Liu, Jinqing Wang, Shengrong Yang
Hydrogels are ideal lubricants due to their hydrophilicity and ability to mitigate issues such as creep and leakage. Based on the diversity of application environments, it is crucial to develop hydrogels with adjustable lubrication that can adjust their lubrication properties by changing in the external environment. However, they still face challenges in balancing responsiveness, lubrication efficacy, and safety. This study presents a pH-responsive hydrogel prepared from polyvinylpyrrolidone and phytic acid, with the addition of MXene and glycerol to enhance its tribological performance. The optimal contents of MXene and glycerol for peak lubrication efficiency are found to be 5 mg/mL and 5 wt %, respectively. This hydrogel lubricant can maintain a low-friction state without failure in long-term testing for 3 h, achieving a coefficient of friction (COF) of 0.01. The synergistic lubrication effect of MXene and glycerol reached a friction reduction of 69% and a wear resistance improvement of up to 96%. Moreover, the COF can be regulated by adjusting the pH value. This hydrogel also stands out with its robust self-healing, injectability, and biocompatibility, making it an excellent candidate for advanced lubrication in biomedical applications.
{"title":"Injectable and Self-Healing MXene-Reinforced pH-Responsive Hydrogel: Realizing Low-Friction and Durable Lubrication","authors":"Yan Huang, Zhangpeng Li, Yaochen Wang, Qiulong Gao, Kaiming Hou, Shuwen Liu, Jinqing Wang, Shengrong Yang","doi":"10.1021/acssuschemeng.4c07993","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07993","url":null,"abstract":"Hydrogels are ideal lubricants due to their hydrophilicity and ability to mitigate issues such as creep and leakage. Based on the diversity of application environments, it is crucial to develop hydrogels with adjustable lubrication that can adjust their lubrication properties by changing in the external environment. However, they still face challenges in balancing responsiveness, lubrication efficacy, and safety. This study presents a pH-responsive hydrogel prepared from polyvinylpyrrolidone and phytic acid, with the addition of MXene and glycerol to enhance its tribological performance. The optimal contents of MXene and glycerol for peak lubrication efficiency are found to be 5 mg/mL and 5 wt %, respectively. This hydrogel lubricant can maintain a low-friction state without failure in long-term testing for 3 h, achieving a coefficient of friction (COF) of 0.01. The synergistic lubrication effect of MXene and glycerol reached a friction reduction of 69% and a wear resistance improvement of up to 96%. Moreover, the COF can be regulated by adjusting the pH value. This hydrogel also stands out with its robust self-healing, injectability, and biocompatibility, making it an excellent candidate for advanced lubrication in biomedical applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832718","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}
Liquid hot water pretreatment (LHWP) can convert hemicellulose in biomass into valuable xylooligosaccharides, but the utilization of glucan in the solid residue after hemicellulose extraction is usually constrained due to the significant lignin condensation during the LHWP. To alleviate lignin’s inhibition on glucan saccharification, this study established a variety of functional deep eutectic solvents (DESs) for the pretreatment of the solid residues after LHWP. The applied DES pretreatments resulted in different glucan saccharification yields. Under the premise of similar lignin removal, the ChCl/ethylene glycol (EG) system obtained near complete glucan digestibility, while the acid or alkali DESs had much lower enzymatic saccharification yields (35.7% and 20.6%). The mechanism of boosting the glucan saccharification by ChCl/EG was comprehensively analyzed by 2D-HSQC NMR, hydrophobicity, GPC and Langmuir adsorption isotherm of enzymes onto the cellulolytic enzyme lignin. Results indicated that lignin remaining in the ChCl/EG pretreated substrates had a lower hydrophobicity (2.8 L/g) and enzyme adsorption (4.6 mg/g), resulting from the EG grafting onto the α-position of the lignin side chain (as high as 5.0/100 Ar). The LHWP-DES pretreatment in this study unveiled the mechanism for cellulose digestibility enhancement using three common DESs and maximized the enzymatic hydrolysis yield, which provided a new scheme for the high-value utilization of biomass.
液态热水预处理（LHWP）可将生物质中的半纤维素转化为有价值的木寡糖，但由于液态热水预处理过程中木质素的大量凝结，通常会限制半纤维素提取后固体残渣中葡聚糖的利用。为了缓解木质素对葡聚糖糖化的抑制作用，本研究建立了多种功能性深共晶溶剂（DES），用于 LHWP 后固体残渣的预处理。所采用的 DES 预处理方法导致了不同的葡聚糖糖化率。在木质素去除率相似的前提下，氯化氢/乙二醇（EG）体系可获得接近完全的葡聚糖消化率，而酸性或碱性 DES 的酶糖化率则低得多（35.7% 和 20.6%）。通过二维-HSQC NMR、疏水性、GPC 和酶对纤维素分解酶木质素的朗缪尔吸附等温线，全面分析了 ChCl/EG 促进葡聚糖糖化的机理。结果表明，ChCl/EG 预处理基质中残留的木质素具有较低的疏水性（2.8 L/g）和酶吸附性（4.6 mg/g），这是由于 EG 接枝到了木质素侧链的 α 位（高达 5.0/100 Ar）。本研究中的 LHWP-DES 预处理揭示了使用三种常见 DESs 提高纤维素消化率的机理，并最大限度地提高了酶水解产率，为生物质的高值化利用提供了一种新方案。
{"title":"Modification of Condensed Lignin by Deep Eutectic Solvents: Insight into the Mechanism of Improving the Enzymatic Saccharification","authors":"Tingjun Chen, Xuelian Zhou, Yunni Zhan, Jinyuan Cheng, Caoxing Huang, Chang Geun Yoo, Guigan Fang, Arthur J. Ragauskas, Xianzhi Meng, Chen Huang","doi":"10.1021/acssuschemeng.4c05937","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05937","url":null,"abstract":"Liquid hot water pretreatment (LHWP) can convert hemicellulose in biomass into valuable xylooligosaccharides, but the utilization of glucan in the solid residue after hemicellulose extraction is usually constrained due to the significant lignin condensation during the LHWP. To alleviate lignin’s inhibition on glucan saccharification, this study established a variety of functional deep eutectic solvents (DESs) for the pretreatment of the solid residues after LHWP. The applied DES pretreatments resulted in different glucan saccharification yields. Under the premise of similar lignin removal, the ChCl/ethylene glycol (EG) system obtained near complete glucan digestibility, while the acid or alkali DESs had much lower enzymatic saccharification yields (35.7% and 20.6%). The mechanism of boosting the glucan saccharification by ChCl/EG was comprehensively analyzed by 2D-HSQC NMR, hydrophobicity, GPC and Langmuir adsorption isotherm of enzymes onto the cellulolytic enzyme lignin. Results indicated that lignin remaining in the ChCl/EG pretreated substrates had a lower hydrophobicity (2.8 L/g) and enzyme adsorption (4.6 mg/g), resulting from the EG grafting onto the α-position of the lignin side chain (as high as 5.0/100 Ar). The LHWP-DES pretreatment in this study unveiled the mechanism for cellulose digestibility enhancement using three common DESs and maximized the enzymatic hydrolysis yield, which provided a new scheme for the high-value utilization of biomass.","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":"142832662","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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