Simultaneous utilization of lignocellulose-related glucose and xylose to produce methyl levulinate (ML), a versatile industrial commodity, is important to fully expend biomass components. We herein report a promising catalytic protocol involving the Hβ zeolite in dimethoxymethane (DMM) and methanol (MeOH) cosolvent that enables the coconversion of glucose and xylose to ML under one-pot conditions. ML yield as high as 56% with a turnover frequency (TOF) of over 3.2 h–1 can be accomplished at 150 °C. Isomerization–dehydration of glucose/xylose represents the primary reaction path, whereas the production of glycosides through etherification constitutes the secondary reaction path. The suggested catalytic mechanism is the preferential adsorption of C–O–C and C–OH groups at different acid sites, which leads to the emergence of two distinct pathways for the conversion of glucose/xylose into ML. Hβ-25, featuring a high concentration of Lewis and Brønsted acid sites, facilitates two distinct pathways for the conversion of glucose/xylose into ML. DMM functions as a hydroxymethylation reagent in the conversion of xylose to ML and promotes the isomerization of glycosides via ether exchange reactions. This contribution devises an efficient strategy for producing ML from glucose and xylose while elucidating the reaction mechanism of a tailored monolithic catalytic system.
{"title":"Understanding How Hβ Zeolite in Dimethoxymethane-Containing Medium Efficiently Coconverts Glucose and Xylose to Methyl Levulinate","authors":"Yu Zhang, Huai Liu, Rui Zhang, Wenlong Jia, Junhua Zhang, Lincai Peng","doi":"10.1021/acssuschemeng.5c00272","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00272","url":null,"abstract":"Simultaneous utilization of lignocellulose-related glucose and xylose to produce methyl levulinate (ML), a versatile industrial commodity, is important to fully expend biomass components. We herein report a promising catalytic protocol involving the Hβ zeolite in dimethoxymethane (DMM) and methanol (MeOH) cosolvent that enables the coconversion of glucose and xylose to ML under one-pot conditions. ML yield as high as 56% with a turnover frequency (TOF) of over 3.2 h<sup>–1</sup> can be accomplished at 150 °C. Isomerization–dehydration of glucose/xylose represents the primary reaction path, whereas the production of glycosides through etherification constitutes the secondary reaction path. The suggested catalytic mechanism is the preferential adsorption of C–O–C and C–OH groups at different acid sites, which leads to the emergence of two distinct pathways for the conversion of glucose/xylose into ML. Hβ-25, featuring a high concentration of Lewis and Brønsted acid sites, facilitates two distinct pathways for the conversion of glucose/xylose into ML. DMM functions as a hydroxymethylation reagent in the conversion of xylose to ML and promotes the isomerization of glycosides via ether exchange reactions. This contribution devises an efficient strategy for producing ML from glucose and xylose while elucidating the reaction mechanism of a tailored monolithic catalytic system.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"64 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857560","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 : 2025-04-22DOI: 10.1021/acssuschemeng.5c01330
Gloria Rosetto, Katherine A. Chism, Luana Cardinale, Daria Lazarenko, Julia B. Curley, Kevin M. Wernke, Levi J. Hamernik, Clarissa Lincoln, Stefan J. Haugen, Kelsey J. Ramirez, Mikhail O. Konev, Xuan Liu, Brandon C. Knott, Nicholas A. Rorrer, Shannon S. Stahl, Gregg T. Beckham
Lignin-derived aromatic carboxylic acids can be produced from oxidative catalytic processes and are promising building blocks for performance-advantaged bioproducts that leverage their inherent heteroatom functionalities. Here, we synthesize 2-methoxyterephthalate and 2,6-dimethoxyterephthalate derivatives by electrochemical carboxylation of guaiacyl- and syringyl-derived lignin monomers obtained from the oxidative deconstruction of lignin. These methoxylated terephthalates are evaluated as comonomers in poly(ethylene terephthalate) (PET) and as plasticizers that could replace petrochemically-derived isophthalate and phthalate, respectively. Specifically, we copolymerize 2-methoxy- and 2,6-dimethoxyterephthalate with dimethyl terephthalate to form several PET copolymers, both of which enable the properties of PET to be tuned, with an incorporation beyond 25% producing amorphous polyesters. At 10 mol % loading in the copolymers, we demonstrate that the bioderived comonomers exhibit comparable behavior to isophthalic acid, a commonly used comonomer in PET, by lowering the crystallinity and melting temperature. Moreover, methoxyterephthalate esters (2-ethylhexyl and butyl) are compared to phthalate and terephthalate ester counterparts used as poly(vinyl chloride) (PVC) plasticizers. The bioderived plasticizers are comparable to the petroleum-derived incumbents in reducing the glass transition temperature and increasing the thermal stability of PVC. Furthermore, the dimethoxyterephthalic esters are expected to have an extended lifetime in the polymer matrix due to their lower volatility and lower diffusion coefficients calculated by molecular dynamic simulations. These results demonstrate that the isophthalate and phthalate components in polyesters and plasticizers, respectively, could be substituted with biobased methoxyterephthalate derivatives.
{"title":"Lignin-Derived Methoxyterephthalates for Performance-Advantaged Polymers and Plasticizers","authors":"Gloria Rosetto, Katherine A. Chism, Luana Cardinale, Daria Lazarenko, Julia B. Curley, Kevin M. Wernke, Levi J. Hamernik, Clarissa Lincoln, Stefan J. Haugen, Kelsey J. Ramirez, Mikhail O. Konev, Xuan Liu, Brandon C. Knott, Nicholas A. Rorrer, Shannon S. Stahl, Gregg T. Beckham","doi":"10.1021/acssuschemeng.5c01330","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c01330","url":null,"abstract":"Lignin-derived aromatic carboxylic acids can be produced from oxidative catalytic processes and are promising building blocks for performance-advantaged bioproducts that leverage their inherent heteroatom functionalities. Here, we synthesize 2-methoxyterephthalate and 2,6-dimethoxyterephthalate derivatives by electrochemical carboxylation of guaiacyl- and syringyl-derived lignin monomers obtained from the oxidative deconstruction of lignin. These methoxylated terephthalates are evaluated as comonomers in poly(ethylene terephthalate) (PET) and as plasticizers that could replace petrochemically-derived isophthalate and phthalate, respectively. Specifically, we copolymerize 2-methoxy- and 2,6-dimethoxyterephthalate with dimethyl terephthalate to form several PET copolymers, both of which enable the properties of PET to be tuned, with an incorporation beyond 25% producing amorphous polyesters. At 10 mol % loading in the copolymers, we demonstrate that the bioderived comonomers exhibit comparable behavior to isophthalic acid, a commonly used comonomer in PET, by lowering the crystallinity and melting temperature. Moreover, methoxyterephthalate esters (2-ethylhexyl and butyl) are compared to phthalate and terephthalate ester counterparts used as poly(vinyl chloride) (PVC) plasticizers. The bioderived plasticizers are comparable to the petroleum-derived incumbents in reducing the glass transition temperature and increasing the thermal stability of PVC. Furthermore, the dimethoxyterephthalic esters are expected to have an extended lifetime in the polymer matrix due to their lower volatility and lower diffusion coefficients calculated by molecular dynamic simulations. These results demonstrate that the isophthalate and phthalate components in polyesters and plasticizers, respectively, could be substituted with biobased methoxyterephthalate derivatives.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857562","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 : 2025-04-22DOI: 10.1021/acssuschemeng.5c00986
Mariyam Mukhtarova, Maria A. Golubeva, Anton L. Maximov
The development of an effective approach for plastic recycling using a highly active catalytic system represents a crucial step toward reducing the harmful impact of plastic waste on the environment. This work described the comparison of the catalytic performance of in situ formed molybdenum and tungsten phosphides and oxides in the hydroprocessing of such widely used plastics as polyethylene terephthalate and its intermediate conversion products (various carboxylic acids). MoP and MoOx catalysts promoted conversion of PET toward p-xylene (69% over MoP and 86% over MoOx at full PET conversion). In the presence of WP and WOx catalysts, the formation of a mixture of toluene and p-xylene with selectivities of 55% and 77% at 100% PET conversion was observed. The possibility of reusing catalysts in PET processing during five test runs for MoOx and WOx and during three test runs for MoP and WP without significant loss of activity was shown. The obtained catalysts were characterized by XRD, XPS, HRTEM, EDX, and NH3–TPD methods. In addition, a correspondence between the different nature of the active sites and the composition of the reaction products for various catalysts is presented.
{"title":"Comparison of In Situ Formed Metal (Mo, W) Phosphides and Oxides in the Hydroprocessing of Used PET Bottles","authors":"Mariyam Mukhtarova, Maria A. Golubeva, Anton L. Maximov","doi":"10.1021/acssuschemeng.5c00986","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00986","url":null,"abstract":"The development of an effective approach for plastic recycling using a highly active catalytic system represents a crucial step toward reducing the harmful impact of plastic waste on the environment. This work described the comparison of the catalytic performance of <i>in situ</i> formed molybdenum and tungsten phosphides and oxides in the hydroprocessing of such widely used plastics as polyethylene terephthalate and its intermediate conversion products (various carboxylic acids). MoP and MoO<sub><i>x</i></sub> catalysts promoted conversion of PET toward <i>p</i>-xylene (69% over MoP and 86% over MoO<sub><i>x</i></sub> at full PET conversion). In the presence of WP and WO<sub><i>x</i></sub> catalysts, the formation of a mixture of toluene and <i>p</i>-xylene with selectivities of 55% and 77% at 100% PET conversion was observed. The possibility of reusing catalysts in PET processing during five test runs for MoO<sub><i>x</i></sub> and WO<sub><i>x</i></sub> and during three test runs for MoP and WP without significant loss of activity was shown. The obtained catalysts were characterized by XRD, XPS, HRTEM, EDX, and NH<sub>3</sub>–TPD methods. In addition, a correspondence between the different nature of the active sites and the composition of the reaction products for various catalysts is presented.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"108 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857561","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 : 2025-04-22DOI: 10.1021/acssuschemeng.5c02071
Yujun Zhou, Nan Nan Xia, Jialu Zhang, Tianxiang Li, Jianmin Wang, Qin Wu
The repeated bonding properties of wood adhesives directly influence the service life of wood. The covalent cross-linked networks of conventional thermosetting wood adhesives endow them with excellent performance but suppress the mobility of molecular chains, hindering the repeated bonding after adhesive failure via molecular chain reorganization. Here, we develop a thermoplastic hyperbranched polyurethane wood adhesive, which contains a prepolymer composed of cashew phenol, polyol, and isocyanate groups as the branching chains, a hyperbranched polyester as the core, and lipoic acid with disulfide (S–S) bonds as the terminal groups. When this adhesive breaks or cracks under external force and the broken surfaces are joined together, the molecular chains on both sides of the adhesive converge toward the breakage points driven by the highly branched structure of the hyperbranched polymer, promoting contact between the S–S bonds on both sides. Under heating conditions, dynamic reversible exchange reactions occur, stitching the cracks, and enabling the adhesive to bond repeatedly. Benefiting from this advantage, HPU-LA (100%) can retain more than 85% of its original bonding strength even after undergoing five repeated bonding cycles at 80 °C. This study addresses the issue of resource waste caused by the nonreusability of conventional adhesives as well as has notable research implications for extending the service life of wood.
{"title":"Novel Reusable Wood Adhesive Comprising Disulfide Bond–Modified Polyurethane","authors":"Yujun Zhou, Nan Nan Xia, Jialu Zhang, Tianxiang Li, Jianmin Wang, Qin Wu","doi":"10.1021/acssuschemeng.5c02071","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c02071","url":null,"abstract":"The repeated bonding properties of wood adhesives directly influence the service life of wood. The covalent cross-linked networks of conventional thermosetting wood adhesives endow them with excellent performance but suppress the mobility of molecular chains, hindering the repeated bonding after adhesive failure via molecular chain reorganization. Here, we develop a thermoplastic hyperbranched polyurethane wood adhesive, which contains a prepolymer composed of cashew phenol, polyol, and isocyanate groups as the branching chains, a hyperbranched polyester as the core, and lipoic acid with disulfide (S–S) bonds as the terminal groups. When this adhesive breaks or cracks under external force and the broken surfaces are joined together, the molecular chains on both sides of the adhesive converge toward the breakage points driven by the highly branched structure of the hyperbranched polymer, promoting contact between the S–S bonds on both sides. Under heating conditions, dynamic reversible exchange reactions occur, stitching the cracks, and enabling the adhesive to bond repeatedly. Benefiting from this advantage, HPU-LA (100%) can retain more than 85% of its original bonding strength even after undergoing five repeated bonding cycles at 80 <i>°C</i>. This study addresses the issue of resource waste caused by the nonreusability of conventional adhesives as well as has notable research implications for extending the service life of wood.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857563","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 : 2025-04-22DOI: 10.1021/acssuschemeng.4c09995
Jiayi Wang, Yichen Hao, Jinping Li, Jiangfeng Yang
The shortage of lithium resources and the accumulation of retired batteries are strategic issues that need to be addressed urgently. Here, we propose an innovative and efficient strategy for the preferential extraction of Li+, followed by the sequential recovery of Mn2+ and Co2+, utilizing GIS zeolite from battery leachate. Li+ ions were preferentially exchanged, achieving a 95% recovery rate at 0 °C; subsequently, 94% of Mn2+ and 97% of Co2+ were recovered by increasing the temperature to 40 and 60 °C; meanwhile, 90% of Ni2+ remains in solution. The fastest kinetic rate of Li+ in GIS zeolite and its efficient extraction at low temperatures were verified through ion exchange processes; at higher temperatures, the adsorption capacity and selectivity of GIS zeolite for Co2+ and Mn2+ increased. We found the diffusion rate of Li+ in GIS zeolite to be over 2.5 times faster than that of Mn2+, Co2+, and Ni2+, which all have the same rate by molecular dynamics simulations. The ion exchange of Mn2+, Co2+, and Ni2+ was an endothermic reaction, with the ΔH0 and ΔG0 following the order Mn2+ < Co2+ < Ni2+ by thermodynamic calculations. The regeneration ability of GIS zeolite indicated its promising industrial application prospects.
{"title":"Priority Extraction of Li+ and Sequential Recovery of Divalent Metals from Retired LiNixCoyMn1–x–yO2 Batteries Using GIS Zeolite","authors":"Jiayi Wang, Yichen Hao, Jinping Li, Jiangfeng Yang","doi":"10.1021/acssuschemeng.4c09995","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09995","url":null,"abstract":"The shortage of lithium resources and the accumulation of retired batteries are strategic issues that need to be addressed urgently. Here, we propose an innovative and efficient strategy for the preferential extraction of Li<sup>+</sup>, followed by the sequential recovery of Mn<sup>2+</sup> and Co<sup>2+</sup>, utilizing GIS zeolite from battery leachate. Li<sup>+</sup> ions were preferentially exchanged, achieving a 95% recovery rate at 0 °C; subsequently, 94% of Mn<sup>2+</sup> and 97% of Co<sup>2+</sup> were recovered by increasing the temperature to 40 and 60 °C; meanwhile, 90% of Ni<sup>2+</sup> remains in solution. The fastest kinetic rate of Li<sup>+</sup> in GIS zeolite and its efficient extraction at low temperatures were verified through ion exchange processes; at higher temperatures, the adsorption capacity and selectivity of GIS zeolite for Co<sup>2+</sup> and Mn<sup>2+</sup> increased. We found the diffusion rate of Li<sup>+</sup> in GIS zeolite to be over 2.5 times faster than that of Mn<sup>2+</sup>, Co<sup>2+</sup>, and Ni<sup>2+</sup>, which all have the same rate by molecular dynamics simulations. The ion exchange of Mn<sup>2+</sup>, Co<sup>2+</sup>, and Ni<sup>2+</sup> was an endothermic reaction, with the Δ<i>H</i><sup>0</sup> and Δ<i>G</i><sup>0</sup> following the order Mn<sup>2+</sup> < Co<sup>2+</sup> < Ni<sup>2+</sup> by thermodynamic calculations. The regeneration ability of GIS zeolite indicated its promising industrial application prospects.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857559","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 : 2025-04-22DOI: 10.1021/acssuschemeng.5c02289
Sri Hari Anandhi Rajendran, Sabrina Kogler, Philipp Kögl, Wilfried M. Braje, Sándor B. Ötvös, C. Oliver Kappe
The widespread use of peptide-based drugs and the prevalence of amide-containing pharmaceuticals underscore the critical need for efficient, sustainable, and environmentally friendly amidation methods in the pharmaceutical industry. However, traditional approaches rely on harmful solvents, highlighting the urgent need for a paradigm shift toward greener alternatives. We leveraged continuous slurry flow technology to facilitate solid handling and develop scalable and sustainable protocols for amide bond formation in water as the reaction medium. To ensure optimal mass transfer through efficient active mixing, we utilized a spinning disc reactor and an agitated continuous stirred-tank reactor series, both of which are commercially available, including industrial-scale versions. As model reactions, we selected the synthesis of a key efaproxiral intermediate and a technically challenging amidation involving a protected tryptophan derivative. The best results were achieved using hydroxypropyl methylcellulose, a cost-effective, nontoxic, cellulose-derived surface-active agent in water. The optimized lab-scale protocols enabled rapid amidations with productivities of up to 2 kg per day. Notably, neither the synthesis nor the isolation processes required any organic solvents, resulting in minimal waste generation.
{"title":"Sustainable and Scalable Amidations in Water Using Continuous Slurry-Flow Technology","authors":"Sri Hari Anandhi Rajendran, Sabrina Kogler, Philipp Kögl, Wilfried M. Braje, Sándor B. Ötvös, C. Oliver Kappe","doi":"10.1021/acssuschemeng.5c02289","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c02289","url":null,"abstract":"The widespread use of peptide-based drugs and the prevalence of amide-containing pharmaceuticals underscore the critical need for efficient, sustainable, and environmentally friendly amidation methods in the pharmaceutical industry. However, traditional approaches rely on harmful solvents, highlighting the urgent need for a paradigm shift toward greener alternatives. We leveraged continuous slurry flow technology to facilitate solid handling and develop scalable and sustainable protocols for amide bond formation in water as the reaction medium. To ensure optimal mass transfer through efficient active mixing, we utilized a spinning disc reactor and an agitated continuous stirred-tank reactor series, both of which are commercially available, including industrial-scale versions. As model reactions, we selected the synthesis of a key efaproxiral intermediate and a technically challenging amidation involving a protected tryptophan derivative. The best results were achieved using hydroxypropyl methylcellulose, a cost-effective, nontoxic, cellulose-derived surface-active agent in water. The optimized lab-scale protocols enabled rapid amidations with productivities of up to 2 kg per day. Notably, neither the synthesis nor the isolation processes required any organic solvents, resulting in minimal waste generation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"68 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857565","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 : 2025-04-21DOI: 10.1021/acssuschemeng.4c10451
Claire Morand, Daniele Mantione, Andrew P. Dove, Haritz Sardón, Coralie Jehanno
Replacing fossil-derived polymers with biobased alternatives is essential to reduce the environmental impact of plastics production, as it helps to decrease reliance on finite fossil resources and promotes sustainability by using renewable raw materials. However, biobased options remain scarce in the industry, as it is difficult to produce fully biobased polymers at a reasonable cost with the same functional properties. In this study, 100% biobased unsaturated polyesters are synthesized from maleic acid and 1,3-propanediol through bulk polycondensation mediated by biosourced catalysts. The resulting materials present different degrees of double bond isomerization depending on the catalyst employed, with higher trans content obtained using catalysts that exhibit greater nucleophilicity. With the objective of using these polyester resins for additive manufacturing, the reactivity of the double bonds was analyzed through FTIR and photo-DSC, while the cross-linking process was studied by photorheology, which highlighted the superior reactivity of the trans double bonds. This study opens avenues for the synthesis of 100% biosourced polyester resins with tunable cis/trans content.
{"title":"Controlling the cis/trans Content of Biobased Unsaturated Polyesters by Judicious Choice of a Biosourced Catalyst","authors":"Claire Morand, Daniele Mantione, Andrew P. Dove, Haritz Sardón, Coralie Jehanno","doi":"10.1021/acssuschemeng.4c10451","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10451","url":null,"abstract":"Replacing fossil-derived polymers with biobased alternatives is essential to reduce the environmental impact of plastics production, as it helps to decrease reliance on finite fossil resources and promotes sustainability by using renewable raw materials. However, biobased options remain scarce in the industry, as it is difficult to produce fully biobased polymers at a reasonable cost with the same functional properties. In this study, 100% biobased unsaturated polyesters are synthesized from maleic acid and 1,3-propanediol through bulk polycondensation mediated by biosourced catalysts. The resulting materials present different degrees of double bond isomerization depending on the catalyst employed, with higher <i>trans</i> content obtained using catalysts that exhibit greater nucleophilicity. With the objective of using these polyester resins for additive manufacturing, the reactivity of the double bonds was analyzed through FTIR and photo-DSC, while the cross-linking process was studied by photorheology, which highlighted the superior reactivity of the <i>trans</i> double bonds. This study opens avenues for the synthesis of 100% biosourced polyester resins with tunable <i>cis/trans</i> content.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"66 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853691","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}
Agricultural biomass such as rice straws represents a significant volume of waste generated worldwide; disposal of which through landfilling and burning is a major global challenge. In the present study, strategic functionalization of rice straws through delignification-cum-phosphorylation using low-cost agrochemicals followed by scalable processing into films and beverage cups is developed. The phosphorylated films with high charge content (1488–2199 mmol kg–1) show improved mechanical strength under both dry and wet conditions with high thermal stability and flame retardancy. A detailed mechanistic study using FTIR and XPS spectroscopy confirmed the covalently bonded phosphate groups on the cellulose backbone along with the formation of silicon phosphate cross-linkages upon heating. Interestingly, the all-cellulose films could be heat-sealed, improving the shelf life of highly perishable stored fruits and vegetables. Molded cups demonstrate high solvothermal stability with antifizzing and improved washability (for 3 times) post consumption. The proposed valorization of rice straws into packaging films and beverage cups with lower ecological impacts and commercial feasibility provides a sustainable alternative for a plastic-free world.
{"title":"All-Biomass-Derived Cellulose Phosphate-Based Heat-Sealable Films and Thermally Stable Antifizzing Cups with Improved Recyclability","authors":"Rahul Ranjan, Vedang P. Mone, Rohit Rai, Chandra Kant, Prodyut Dhar","doi":"10.1021/acssuschemeng.4c09105","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09105","url":null,"abstract":"Agricultural biomass such as rice straws represents a significant volume of waste generated worldwide; disposal of which through landfilling and burning is a major global challenge. In the present study, strategic functionalization of rice straws through delignification-<i>cum</i>-phosphorylation using low-cost agrochemicals followed by scalable processing into films and beverage cups is developed. The phosphorylated films with high charge content (1488–2199 mmol kg<sup>–1</sup>) show improved mechanical strength under both dry and wet conditions with high thermal stability and flame retardancy. A detailed mechanistic study using FTIR and XPS spectroscopy confirmed the covalently bonded phosphate groups on the cellulose backbone along with the formation of silicon phosphate cross-linkages upon heating. Interestingly, the all-cellulose films could be heat-sealed, improving the shelf life of highly perishable stored fruits and vegetables. Molded cups demonstrate high solvothermal stability with antifizzing and improved washability (for 3 times) post consumption. The proposed valorization of rice straws into packaging films and beverage cups with lower ecological impacts and commercial feasibility provides a sustainable alternative for a plastic-free world.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857460","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 : 2025-04-21DOI: 10.1021/acssuschemeng.4c07823
Lilian C. Alarcón-Segovia, Kenneth E. Madsen, Claire Liu, Sun Hong Kim, Tae Wan Park, Yayun Du, Joanna L. Ciatti, Kathrin H. Salame, Jae-Young Yoo, John A. Rogers
Global access to quality healthcare remains one of the most pressing issues for modern society. Despite advances in wearable and point-of-care biomedical devices, the dissemination of these technologies to resource-limited populations remains challenging, partially due to limitations imposed by cost. One of the largest cost drivers in the adoption of wearable devices for electrophysiological (ExG) monitoring, for instance, is the consumable overhead (electrolytes, adhesives, and electrodes) necessary to support patient use. Herein, we report the development and optimization of ultralow-cost (<0.03 USD per electrode), stable, and resource-available ExG electrolytes fabricated from agricultural byproducts widely available in local settings, thereby negating the dependency on importation. We show that composite hydrogels can be prepared from a variety of starch precursors via a facile one-pot sol–gel method to yield ionically conductive, mechanically compliant gel electrolytes. We further demonstrate that food starch materials for these purposes are resistant to dehydration and, when coupled with a wireless recording platform, can facilitate long-term (8 h) signal recording without significant loss in signal quality. Together, these characteristics mark starch-based electrolytes as possible alternatives to commercial formulations for skin-interfaced measurement electrodes, compatible with mobile sensing apparatus in resource-limited settings with cost, sustainability, and supply chain advantages without sacrificing clinical performance.
{"title":"Ultralow-Cost Hydrogel Electrolytes Based on Agricultural Byproducts for Distributed Electrophysiological Recording in Resource-Limited Settings","authors":"Lilian C. Alarcón-Segovia, Kenneth E. Madsen, Claire Liu, Sun Hong Kim, Tae Wan Park, Yayun Du, Joanna L. Ciatti, Kathrin H. Salame, Jae-Young Yoo, John A. Rogers","doi":"10.1021/acssuschemeng.4c07823","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07823","url":null,"abstract":"Global access to quality healthcare remains one of the most pressing issues for modern society. Despite advances in wearable and point-of-care biomedical devices, the dissemination of these technologies to resource-limited populations remains challenging, partially due to limitations imposed by cost. One of the largest cost drivers in the adoption of wearable devices for electrophysiological (ExG) monitoring, for instance, is the consumable overhead (electrolytes, adhesives, and electrodes) necessary to support patient use. Herein, we report the development and optimization of ultralow-cost (<0.03 USD per electrode), stable, and resource-available ExG electrolytes fabricated from agricultural byproducts widely available in local settings, thereby negating the dependency on importation. We show that composite hydrogels can be prepared from a variety of starch precursors via a facile one-pot sol–gel method to yield ionically conductive, mechanically compliant gel electrolytes. We further demonstrate that food starch materials for these purposes are resistant to dehydration and, when coupled with a wireless recording platform, can facilitate long-term (8 h) signal recording without significant loss in signal quality. Together, these characteristics mark starch-based electrolytes as possible alternatives to commercial formulations for skin-interfaced measurement electrodes, compatible with mobile sensing apparatus in resource-limited settings with cost, sustainability, and supply chain advantages without sacrificing clinical performance.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"68 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853692","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 : 2025-04-21DOI: 10.1021/acssuschemeng.4c08815
Rarosue J. Amaraibi, Babu Joseph, John N. Kuhn
This paper conducts a comprehensive life cycle assessment (LCA) of the intensified biogas to liquids (IBGTL) process, focusing on its global warming potential (GWP) and comparing it to alternative biogas utilization pathways. Landfill gas (LFG), derived from municipal solid waste (MSW) decomposition, contributes significantly to methane emissions and poses environmental risks. Regulatory initiatives promote LFG capture and utilization for renewable energy production. The IBGTL process, integrating bi-reforming and Fischer–Tropsch synthesis into a compact reactor design, offers advantages in reduced capital and operating costs. This study quantifies the life cycle impacts of IBGTL diesel production and benchmarks it against other LFG utilization routes, including TriFTS diesel, LFG to electricity, and LFG to compressed renewable natural gas. Using a “well-to-wheel” boundary, the study evaluates emissions from production to usage. Findings indicate substantial reductions in greenhouse gas (GHG) emissions across all LFG-to-energy pathways compared to fossil alternatives, with the most significant savings achieved by IBGTL diesel with electricity cogeneration (Scenario 4, 221 gCO2eq/MJ reduction), followed by LFG to electricity (159 gCO2eq/MJ reduction), TriFTS diesel (107 gCO2eq/MJ reduction), and IBGTL diesel with material recycling (Scenario 2, 91.6 gCO2eq/MJ reduction). Sensitivity analyses reveal nuances in emissions impacts. The results highlight the importance of process optimization and grid characteristics in shaping the environmental performance. This research contributes insights for decision-makers, informing sustainable waste management strategies and guiding future LFG-to-energy technologies.
{"title":"Life Cycle Assessment of Liquid Transportation Fuel Produced by the Intensified Biogas to Liquid (IBGTL) Process","authors":"Rarosue J. Amaraibi, Babu Joseph, John N. Kuhn","doi":"10.1021/acssuschemeng.4c08815","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08815","url":null,"abstract":"This paper conducts a comprehensive life cycle assessment (LCA) of the intensified biogas to liquids (IBGTL) process, focusing on its global warming potential (GWP) and comparing it to alternative biogas utilization pathways. Landfill gas (LFG), derived from municipal solid waste (MSW) decomposition, contributes significantly to methane emissions and poses environmental risks. Regulatory initiatives promote LFG capture and utilization for renewable energy production. The IBGTL process, integrating bi-reforming and Fischer–Tropsch synthesis into a compact reactor design, offers advantages in reduced capital and operating costs. This study quantifies the life cycle impacts of IBGTL diesel production and benchmarks it against other LFG utilization routes, including TriFTS diesel, LFG to electricity, and LFG to compressed renewable natural gas. Using a “well-to-wheel” boundary, the study evaluates emissions from production to usage. Findings indicate substantial reductions in greenhouse gas (GHG) emissions across all LFG-to-energy pathways compared to fossil alternatives, with the most significant savings achieved by IBGTL diesel with electricity cogeneration (Scenario 4, 221 gCO<sub>2</sub>eq/MJ reduction), followed by LFG to electricity (159 gCO<sub>2</sub>eq/MJ reduction), TriFTS diesel (107 gCO<sub>2</sub>eq/MJ reduction), and IBGTL diesel with material recycling (Scenario 2, 91.6 gCO<sub>2</sub>eq/MJ reduction). Sensitivity analyses reveal nuances in emissions impacts. The results highlight the importance of process optimization and grid characteristics in shaping the environmental performance. This research contributes insights for decision-makers, informing sustainable waste management strategies and guiding future LFG-to-energy technologies.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857566","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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