Pub Date : 2026-02-09DOI: 10.1021/acssuschemeng.5c11680
Xingqian Wang,Di Zhang,Zehong Chen,Qiaolin Ren,Jiaxin Wang,Wenjun Yan,Jiaqi Qin,Zhongde Wang
The O2 sensitivity of electroactive organic quinone molecules in the field of electrochemical-mediated carbon capture (EMCC) restricts their electrochemical CO2 capture/release process. In this work, 9,10-Phenanthrenequinone (PAQ) was chosen as a capture carrier to precisely regulate the half-wave potential E1/2(Q–1/Q–2) and the CO2 binding constant KCO2 through intermolecular hydrogen-bonding networks between alcohols and reducing quinones. The electrochemical behavior of PAQ was systematically evaluated when different alcohol hydrogen-bond donors were introduced. A Hammett equation was constructed for alcohol hydrogen-bonding systems to quantify the theoretical relationship between electronic structure parameters and macroscopic electrochemical properties of alcohol alkyl groups. The experimental results indicated that proton donors with smaller pKa values and steric hindrance were more likely to form stable intermolecular hydrogen-bonding networks with reduced quinones. Density functional theory confirmed that hydrogen-bond networks obviously reduce the free energy of the inherent reaction system of PAQ, which is the main reason for achieving a better balance of the two key parameters. When the ethanol (EtOH) concentration was 0.66 M, the E1/2(Q–1/Q–2) of PAQ anodically shifted to −0.85 V vs Ag/AgCl; simultaneously, an appropriate Log(KCO2) (8.55) was still maintained at this time, and the estimated minimum energy consumption of the electrochemical system was 50.94 kJ/mol, which was significantly lower than that of the original electrolyte (73.43 kJ/mol). This suggested that constructing intermolecular hydrogen-bonding networks is beneficial for alleviating the O2 stability problem of quinone molecules with strong CO2 complexation.
{"title":"Tuning the Half-Wave Potential and Binding Constant of PAQ Molecules for the Enhanced O2-Tolerant Electrochemical CO2 Capture Process","authors":"Xingqian Wang,Di Zhang,Zehong Chen,Qiaolin Ren,Jiaxin Wang,Wenjun Yan,Jiaqi Qin,Zhongde Wang","doi":"10.1021/acssuschemeng.5c11680","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11680","url":null,"abstract":"The O2 sensitivity of electroactive organic quinone molecules in the field of electrochemical-mediated carbon capture (EMCC) restricts their electrochemical CO2 capture/release process. In this work, 9,10-Phenanthrenequinone (PAQ) was chosen as a capture carrier to precisely regulate the half-wave potential E1/2(Q–1/Q–2) and the CO2 binding constant KCO2 through intermolecular hydrogen-bonding networks between alcohols and reducing quinones. The electrochemical behavior of PAQ was systematically evaluated when different alcohol hydrogen-bond donors were introduced. A Hammett equation was constructed for alcohol hydrogen-bonding systems to quantify the theoretical relationship between electronic structure parameters and macroscopic electrochemical properties of alcohol alkyl groups. The experimental results indicated that proton donors with smaller pKa values and steric hindrance were more likely to form stable intermolecular hydrogen-bonding networks with reduced quinones. Density functional theory confirmed that hydrogen-bond networks obviously reduce the free energy of the inherent reaction system of PAQ, which is the main reason for achieving a better balance of the two key parameters. When the ethanol (EtOH) concentration was 0.66 M, the E1/2(Q–1/Q–2) of PAQ anodically shifted to −0.85 V vs Ag/AgCl; simultaneously, an appropriate Log(KCO2) (8.55) was still maintained at this time, and the estimated minimum energy consumption of the electrochemical system was 50.94 kJ/mol, which was significantly lower than that of the original electrolyte (73.43 kJ/mol). This suggested that constructing intermolecular hydrogen-bonding networks is beneficial for alleviating the O2 stability problem of quinone molecules with strong CO2 complexation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138387","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 : 2026-02-09DOI: 10.1021/acssuschemeng.5c13505
Qiuxia Feng,Liming Zhang,Xinjing Zhang,Zhongwei Cao,Hongbo Li,Peng Zhang,Xuefeng Zhu,Weishen Yang
Proton-conducting ceramics have emerged as a transformative solution for next-generation solid oxide fuel cells for their superior protonic conductivity and high fuel efficiency at intermediate-to-low temperatures. Cobalt-based perovskite oxides stand out as the dominant cathode materials for proton-conducting ceramic fuel cells (PCFCs) due to their unparalleled oxygen reduction reaction activity. However, their implementation is constrained by limited natural reserves and high production costs. To address these challenges, we developed a series of cobalt-free BaFe0.8Zr0.2–xGdxO3−δ (BFZGx, x = 0–0.20) cathodes for low-cost PCFCs. Gd doping simultaneously enhanced the oxygen vacancy concentration and proton hydration capacity while also boosting the total conductivity, with an optimal doping amount of 0.1. Electrochemical evaluations demonstrate the outstanding performance of the BFZGx electrodes, with BaFe0.8Zr0.1Gd0.1O3−δ achieving a 1.93-fold power density compared to the undoped counterpart. This work establishes Gd-doped BaFe0.8Zr0.2O3−δ perovskites as promising high-performance and cost-effective cathode materials for PCFCs.
{"title":"Synergistic Modulation of Oxygen Vacancies and Proton Hydration in Iron-Based Perovskites for Protonic Ceramic Fuel Cells","authors":"Qiuxia Feng,Liming Zhang,Xinjing Zhang,Zhongwei Cao,Hongbo Li,Peng Zhang,Xuefeng Zhu,Weishen Yang","doi":"10.1021/acssuschemeng.5c13505","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13505","url":null,"abstract":"Proton-conducting ceramics have emerged as a transformative solution for next-generation solid oxide fuel cells for their superior protonic conductivity and high fuel efficiency at intermediate-to-low temperatures. Cobalt-based perovskite oxides stand out as the dominant cathode materials for proton-conducting ceramic fuel cells (PCFCs) due to their unparalleled oxygen reduction reaction activity. However, their implementation is constrained by limited natural reserves and high production costs. To address these challenges, we developed a series of cobalt-free BaFe0.8Zr0.2–xGdxO3−δ (BFZGx, x = 0–0.20) cathodes for low-cost PCFCs. Gd doping simultaneously enhanced the oxygen vacancy concentration and proton hydration capacity while also boosting the total conductivity, with an optimal doping amount of 0.1. Electrochemical evaluations demonstrate the outstanding performance of the BFZGx electrodes, with BaFe0.8Zr0.1Gd0.1O3−δ achieving a 1.93-fold power density compared to the undoped counterpart. This work establishes Gd-doped BaFe0.8Zr0.2O3−δ perovskites as promising high-performance and cost-effective cathode materials for PCFCs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138882","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}
Thermoset cross-linked polyethylene (XLPE) with a three-dimensional network structure exhibits high-temperature resistance and excellent insulating properties and is widely used for power cables. However, the permanent covalent cross-linked network leads to difficulties in self-healing and recycling after thermoelectric stress damage. Hence, the development of high-performance and ecofriendly XLPE insulation remains a challenging task. Here, two completely distinct dynamic covalent chemistries, fast-dissociative disulfide bond exchange and slow-associative ester exchange reaction, are combined in a polyethylene network to obtain a novel polyethylene covalent adaptable network (PE CAN). The synergistically regulated dynamic reaction rate enables the efficient self-healing and recyclability of PE CANs without compromising mechanical and insulating properties. In particular, the self-healing efficiency reaches 100% after both mechanical damage and corona damage. After three mechanical recycling cycles, the mechanical and insulation properties still reach the original levels. Moreover, the designed structures of PE CANs enhance the breakdown strength to 325.9 kV/mm and reduce electric field distortion to only 9.7% at 50 kV/mm and 70 °C by building deep traps. Therefore, combining associative and dissociative dynamic covalent bonds resolves the contradiction between high performance and sustainability of XLPE, pointing the way to the next generation of high-voltage direct-current cables.
{"title":"Fast-Dissociative and Slow-Associative Dual Dynamic Bonds Enable Self-Healing and Recyclable Polyethylene Networks for Sustainable High-Voltage Cable Insulation","authors":"Jiangqiong Wang,Wenye Zhang,Weikang Li,Hongzhe Zhang,Jun-Wei Zha","doi":"10.1021/acssuschemeng.5c11912","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11912","url":null,"abstract":"Thermoset cross-linked polyethylene (XLPE) with a three-dimensional network structure exhibits high-temperature resistance and excellent insulating properties and is widely used for power cables. However, the permanent covalent cross-linked network leads to difficulties in self-healing and recycling after thermoelectric stress damage. Hence, the development of high-performance and ecofriendly XLPE insulation remains a challenging task. Here, two completely distinct dynamic covalent chemistries, fast-dissociative disulfide bond exchange and slow-associative ester exchange reaction, are combined in a polyethylene network to obtain a novel polyethylene covalent adaptable network (PE CAN). The synergistically regulated dynamic reaction rate enables the efficient self-healing and recyclability of PE CANs without compromising mechanical and insulating properties. In particular, the self-healing efficiency reaches 100% after both mechanical damage and corona damage. After three mechanical recycling cycles, the mechanical and insulation properties still reach the original levels. Moreover, the designed structures of PE CANs enhance the breakdown strength to 325.9 kV/mm and reduce electric field distortion to only 9.7% at 50 kV/mm and 70 °C by building deep traps. Therefore, combining associative and dissociative dynamic covalent bonds resolves the contradiction between high performance and sustainability of XLPE, pointing the way to the next generation of high-voltage direct-current cables.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"45 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138883","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}
The application of NH4V4O10 with high theoretical specific capacity is restricted due to irreversible deamination and structural instability during repeated Zn2+ (de)intercalation processes. Previous studies have predominantly utilized the preintercalation of excessive inactive metal ions to partially substitute NH4+ ions, achieving improved cycling stability but at the cost of reduced reversible specific capacity. Herein, a low-content Mg2+ preintercalated NH4V4O10 (MNVO, Mg:V = 0.036:4), without replacing interlayer NH4+ ions, is synthesized to achieve structural stabilization for highly stable zinc-ion storage. Characterization results reveal that the preintercalation of low-content Mg2+ induces favorable morphological and structural effects. MNVO features a 3D hierarchical spherical architecture constructed from curled nanosheets, which can facilitate uniform stress distribution and effectively mitigate structural degradation during prolonged Zn2+ (de)intercalation cycles. More importantly, Ex-situ XRD and XPS results reveal that low-content Mg2+ preintercalation fundamentally suppresses the dual degradation pathways of irreversible deamination and byproduct formation in MNVO, thereby preserving structural integrity. Benefiting from these advantages, MNVO achieves an outstanding capacity retention under both low current density (94% after 500 cycles under 0.5 A g–1) and high current density (94% after 5000 cycles under 5 A g–1). This low-content cation preintercalation strategy offers new insight for developing highly stable layered vanadium-based cathode materials for aqueous zinc-ion batteries.
{"title":"Low-Content Mg2+ Preintercalation-Mediated Structural Stabilization in the NH4V4O10 Cathode Enables Ultrastable Zinc-Ion Storage","authors":"Tiezhong Liu,Huifang Yang,Huazhen Fei,Xingyu Yang,Mengxue Li,Qiang Deng,Tingting Liu,Shuang Hou,Tianwen Huang,Lingzhi Zhao","doi":"10.1021/acssuschemeng.5c11990","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11990","url":null,"abstract":"The application of NH4V4O10 with high theoretical specific capacity is restricted due to irreversible deamination and structural instability during repeated Zn2+ (de)intercalation processes. Previous studies have predominantly utilized the preintercalation of excessive inactive metal ions to partially substitute NH4+ ions, achieving improved cycling stability but at the cost of reduced reversible specific capacity. Herein, a low-content Mg2+ preintercalated NH4V4O10 (MNVO, Mg:V = 0.036:4), without replacing interlayer NH4+ ions, is synthesized to achieve structural stabilization for highly stable zinc-ion storage. Characterization results reveal that the preintercalation of low-content Mg2+ induces favorable morphological and structural effects. MNVO features a 3D hierarchical spherical architecture constructed from curled nanosheets, which can facilitate uniform stress distribution and effectively mitigate structural degradation during prolonged Zn2+ (de)intercalation cycles. More importantly, Ex-situ XRD and XPS results reveal that low-content Mg2+ preintercalation fundamentally suppresses the dual degradation pathways of irreversible deamination and byproduct formation in MNVO, thereby preserving structural integrity. Benefiting from these advantages, MNVO achieves an outstanding capacity retention under both low current density (94% after 500 cycles under 0.5 A g–1) and high current density (94% after 5000 cycles under 5 A g–1). This low-content cation preintercalation strategy offers new insight for developing highly stable layered vanadium-based cathode materials for aqueous zinc-ion batteries.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138386","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 : 2026-02-09DOI: 10.1021/acssuschemeng.5c12646
Jin Yan,Hanqiao Liu,Guoxia Wei,Qianlong Han
To balance environmental compliance and industrial sustainability in flue gas treatment from waste incineration, this study systematically evaluates the application patterns and environmental-economic impacts of eight mainstream technologies based on survey data from more than 300 incineration plants across China. Findings indicate that Selective noncatalytic reduction + semidry + dry + activated carbon injection + bag dust + selective catalytic reduction constitutes the dominant configuration nationwide (accounting for over 50%). Research indicates that the T6(Selective noncatalytic reduction + semidry + dry + activated carbon injection + bag dust + selective catalytic reduction + wet), demonstrates optimal performance across multiple environmental metrics. Considering both operational costs and external costs, the T6 process costs 87.9 CNY, making it the most cost-effective option. Notably, following the implementation of the T6 replacement, NOX emissions will decrease by 8.2 × 104 tons, and SO2 emissions will decrease by 3.87 × 104 tons. It also exhibits the lowest values across key performance indicators such as global warming potential (GWP), primary energy demand, and water use, resulting in the smallest indirect emissions. Scenario simulations indicate that promoting technological iteration effectively reduces acidification potential (AP) and GWP. Scenario 3, featuring T6 replacement, achieves optimal emission reduction efficiency, reducing 2.16 × 104 tons SO2 eq and 2.01 × 105 tons CO2 eq. However, GWP exhibits a complex pattern of rising initially and then declining during this process due to the combination of multiple methods and the use of chemical agents. Furthermore, technology upgrade pathways must be tailored to city scale: first-tier cities with annual incineration volumes exceeding one million tons demonstrate significant economies of scale, while smaller towns require cross-regional collaboration to control costs. This study ultimately provides critical scientific support for developing differentiated technology upgrade strategies to achieve the synergistic goals of pollution reduction and carbon mitigation.
{"title":"A Life Cycle Assessment of Flue Gas Treatment Technologies for Municipal Solid Waste Incineration in China: Cost and Environmental Benefits and Regional Adaptability","authors":"Jin Yan,Hanqiao Liu,Guoxia Wei,Qianlong Han","doi":"10.1021/acssuschemeng.5c12646","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12646","url":null,"abstract":"To balance environmental compliance and industrial sustainability in flue gas treatment from waste incineration, this study systematically evaluates the application patterns and environmental-economic impacts of eight mainstream technologies based on survey data from more than 300 incineration plants across China. Findings indicate that Selective noncatalytic reduction + semidry + dry + activated carbon injection + bag dust + selective catalytic reduction constitutes the dominant configuration nationwide (accounting for over 50%). Research indicates that the T6(Selective noncatalytic reduction + semidry + dry + activated carbon injection + bag dust + selective catalytic reduction + wet), demonstrates optimal performance across multiple environmental metrics. Considering both operational costs and external costs, the T6 process costs 87.9 CNY, making it the most cost-effective option. Notably, following the implementation of the T6 replacement, NOX emissions will decrease by 8.2 × 104 tons, and SO2 emissions will decrease by 3.87 × 104 tons. It also exhibits the lowest values across key performance indicators such as global warming potential (GWP), primary energy demand, and water use, resulting in the smallest indirect emissions. Scenario simulations indicate that promoting technological iteration effectively reduces acidification potential (AP) and GWP. Scenario 3, featuring T6 replacement, achieves optimal emission reduction efficiency, reducing 2.16 × 104 tons SO2 eq and 2.01 × 105 tons CO2 eq. However, GWP exhibits a complex pattern of rising initially and then declining during this process due to the combination of multiple methods and the use of chemical agents. Furthermore, technology upgrade pathways must be tailored to city scale: first-tier cities with annual incineration volumes exceeding one million tons demonstrate significant economies of scale, while smaller towns require cross-regional collaboration to control costs. This study ultimately provides critical scientific support for developing differentiated technology upgrade strategies to achieve the synergistic goals of pollution reduction and carbon mitigation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138881","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 : 2026-02-07DOI: 10.1021/acssuschemeng.5c10207
Moorthi Lokanathan, Vaishnavi Mahadevan, Karthikeyan Selvaraj, Prasanna Ramanan, Arunachalam Arulraj, Mangalaraja Ramalinga Viswanathan, Arun Thirumurugan, Sapana Jadoun, Christopher Salvo, Mathivanan Durai, Francisco V. Herrera Diaz, Mani Durai
We present the creation and assessment of ordered hexagonal donut nanoplates (O-HDP) derived from a Pt2FeCu/C ternary alloy, which serve as a highly effective cathode catalyst for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs). The catalyst was produced using a surfactant-free molten-salt technique and was verified by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses for its ordered face-centered tetragonal lattice with a unique donut-like shape. The electrochemical tests showed an activity increase of nearly 17 times compared to Pt/C, while maintaining stability for up to 50k potential cycles. In the single-cell PEMFC evaluations under H2/O2 conditions, the O-HDP Pt2FeCu/C reached a peak power density of 1.711 W cm–2 at a current density of 3.98 A cm–2 and retained 91% of its maximum performance after 30000 durability cycles. The exceptional activity and long-term stability were attributed to its ordered atomic structure, reduced Pt–Pt spacing, distinctive structural geometry, and synergistic alloying effects, making it a promising candidate for future PEMFC applications. Additionally, the simulation of a PEMFC stack using Matlab/Simscape under the urban dynamometer driving schedule (UDDS) driving cycle successfully replicated the realistic dynamic voltage (380–500 V), power (55–60 kW), and thermal responses, confirming the model’s validity as a replacement for the unavailable hardware. The interconnected electrochemical and thermal behaviors highlighted the importance of thermal management to sustain the stack efficiency and longevity in changing the automotive conditions.
{"title":"Ordered Hexagonal Donut Plate of Pt2FeCu/C Ternary Alloy Nanoparticle as a Pro-Efficient Catalyst for ORR","authors":"Moorthi Lokanathan, Vaishnavi Mahadevan, Karthikeyan Selvaraj, Prasanna Ramanan, Arunachalam Arulraj, Mangalaraja Ramalinga Viswanathan, Arun Thirumurugan, Sapana Jadoun, Christopher Salvo, Mathivanan Durai, Francisco V. Herrera Diaz, Mani Durai","doi":"10.1021/acssuschemeng.5c10207","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10207","url":null,"abstract":"We present the creation and assessment of ordered hexagonal donut nanoplates (O-HDP) derived from a Pt<sub>2</sub>FeCu/C ternary alloy, which serve as a highly effective cathode catalyst for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs). The catalyst was produced using a surfactant-free molten-salt technique and was verified by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses for its ordered face-centered tetragonal lattice with a unique donut-like shape. The electrochemical tests showed an activity increase of nearly 17 times compared to Pt/C, while maintaining stability for up to 50k potential cycles. In the single-cell PEMFC evaluations under H<sub>2</sub>/O<sub>2</sub> conditions, the O-HDP Pt<sub>2</sub>FeCu/C reached a peak power density of 1.711 W cm<sup>–2</sup> at a current density of 3.98 A cm<sup>–2</sup> and retained 91% of its maximum performance after 30000 durability cycles. The exceptional activity and long-term stability were attributed to its ordered atomic structure, reduced Pt–Pt spacing, distinctive structural geometry, and synergistic alloying effects, making it a promising candidate for future PEMFC applications. Additionally, the simulation of a PEMFC stack using Matlab/Simscape under the urban dynamometer driving schedule (UDDS) driving cycle successfully replicated the realistic dynamic voltage (380–500 V), power (55–60 kW), and thermal responses, confirming the model’s validity as a replacement for the unavailable hardware. The interconnected electrochemical and thermal behaviors highlighted the importance of thermal management to sustain the stack efficiency and longevity in changing the automotive conditions.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129698","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 : 2026-02-07DOI: 10.1021/acssuschemeng.5c09126
Alberto José Huertas Alonso, Aleksander Jaworski, Rhoda Afriyie Mensah, Solomon Asante-Okyere, Minna Hakkarainen, Mika Henrikki Sipponen
A novel family of lignin-based thermosets that rely on acetal linkages and do not release hazardous compounds during degradation is proposed as future circular design materials. Poly(ethylene glycol) diisopropenyl ether (PDIP) was utilized as a soft segment to form the acetal linkage with the lignin hydroxyl groups via the addition reaction to the isopropenyl double bond. The use of PDIP instead of previously utilized poly(ethylene glycol) divinyl ether (PDV) prevents the release of harmful acetaldehyde during the acidic hydrolysis of the materials. In addition to the lower toxicity of the degradation products, thermosets with PDIP are more resistant to acidic hydrolysis. Characterization of the thermosets by thermal analysis revealed that the merits of this new lignin-PDIP thermoset extended to increased thermal stability, with Td5%, Td30%, and Ts values of 243–253, 349–363, and 152–155 °C, respectively. Furthermore, the developed materials demonstrated intrinsically lower flammability and reduced heat release potential, paving the way for safer materials with a reduced need for potentially harmful flame retardants. The ease of synthesis and high yields achieved encourage further work toward circular and safe materials solutions based on lignin and PDIP.
{"title":"Lignin-Based Acetal Networks: Safer Degradation Pathways for Acid-, Heat-, and Flame-Resistant Circular Thermosets","authors":"Alberto José Huertas Alonso, Aleksander Jaworski, Rhoda Afriyie Mensah, Solomon Asante-Okyere, Minna Hakkarainen, Mika Henrikki Sipponen","doi":"10.1021/acssuschemeng.5c09126","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09126","url":null,"abstract":"A novel family of lignin-based thermosets that rely on acetal linkages and do not release hazardous compounds during degradation is proposed as future circular design materials. Poly(ethylene glycol) diisopropenyl ether (PDIP) was utilized as a soft segment to form the acetal linkage with the lignin hydroxyl groups via the addition reaction to the isopropenyl double bond. The use of PDIP instead of previously utilized poly(ethylene glycol) divinyl ether (PDV) prevents the release of harmful acetaldehyde during the acidic hydrolysis of the materials. In addition to the lower toxicity of the degradation products, thermosets with PDIP are more resistant to acidic hydrolysis. Characterization of the thermosets by thermal analysis revealed that the merits of this new lignin-PDIP thermoset extended to increased thermal stability, with <i>T</i><sub>d5%</sub>, <i>T</i><sub>d30%</sub>, and <i>T</i><sub>s</sub> values of 243–253, 349–363, and 152–155 °C, respectively. Furthermore, the developed materials demonstrated intrinsically lower flammability and reduced heat release potential, paving the way for safer materials with a reduced need for potentially harmful flame retardants. The ease of synthesis and high yields achieved encourage further work toward circular and safe materials solutions based on lignin and PDIP.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"90 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146134826","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}
The synthesis of amino acids from CO2 as the sole carbon source is a critical goal for sustainable biomanufacturing, offering a green alternative to conventional production methods plagued by greenhouse gas emissions and resource competition. Here, we construct a highly efficient cell-free enzymatic platform for the direct biosynthesis of aspartate from CO2. Our integrated platform couples a carbon-fixing module using the modified reductive glycine pathway (rGlyP) with a custom-designed synthesis cascade that condenses two glycine molecules into aspartate, driven by glycine oxidase and a redesigned b-hydroxyaspartate cycle (BHAC). A key challenge in this multienzyme system is achieving pathway synergy. To address this, we employed an enzyme-constrained static model to rationally design the optimal stoichiometry of the five-enzyme cascade. This computational approach not only boosted the final aspartate yield by over 25% but was also essential in identifying glycine oxidase (Bs-ThiO) as the primary rate-limiting bottleneck. Through systematic optimization of enzymes, reaction conditions, and feeding strategies, the system finally achieved accumulation of 17.3 mM aspartate (2.3 g/L) within 2 h, reaching an exceptional 92% of the model-predicted theoretical yield. This study establishes a powerful and sustainable platform for green amino acid production and showcases the significant potential of combining computational design with cell-free engineering to advance the frontier of CO2-based biomanufacturing.
{"title":"Model-Driven Cell-Free Synthesis of the C4 Amino Acid Aspartate Directly from CO2","authors":"Yongjun Mao, Yudian Zhu, Xudong Wang, Jianming Liu, An-Ping Zeng","doi":"10.1021/acssuschemeng.5c11185","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11185","url":null,"abstract":"The synthesis of amino acids from CO<sub>2</sub> as the sole carbon source is a critical goal for sustainable biomanufacturing, offering a green alternative to conventional production methods plagued by greenhouse gas emissions and resource competition. Here, we construct a highly efficient cell-free enzymatic platform for the direct biosynthesis of aspartate from CO<sub>2</sub>. Our integrated platform couples a carbon-fixing module using the modified reductive glycine pathway (rGlyP) with a custom-designed synthesis cascade that condenses two glycine molecules into aspartate, driven by glycine oxidase and a redesigned b-hydroxyaspartate cycle (BHAC). A key challenge in this multienzyme system is achieving pathway synergy. To address this, we employed an enzyme-constrained static model to rationally design the optimal stoichiometry of the five-enzyme cascade. This computational approach not only boosted the final aspartate yield by over 25% but was also essential in identifying glycine oxidase (<i>Bs</i>-ThiO) as the primary rate-limiting bottleneck. Through systematic optimization of enzymes, reaction conditions, and feeding strategies, the system finally achieved accumulation of 17.3 mM aspartate (2.3 g/L) within 2 h, reaching an exceptional 92% of the model-predicted theoretical yield. This study establishes a powerful and sustainable platform for green amino acid production and showcases the significant potential of combining computational design with cell-free engineering to advance the frontier of CO<sub>2</sub>-based biomanufacturing.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129695","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 : 2026-02-07DOI: 10.1021/acssuschemeng.5c12046
Jun Zhao, Fei Liu, Hao Wen, Yuantong Liu, Shangyan Zhou, Chunliang Yang, Haijiao Xie, Lin Yang
Lithium–sulfur (Li–S) batteries are regarded as one of the most promising next-generation energy storage systems owing to their high specific energy and environmental friendliness. However, their practical application is still hindered by the Lithium polysulfides (LiPSs) shuttle effect and sluggish reaction kinetics. In this work, a sulfur-vacancy-rich NiS2/Ni2P heterostructure catalyst was constructed through a combined hydrothermal and vapor phosphorization process and employed to functionalize the separator surface. The sulfur vacancies act as strong adsorption centers that effectively anchor dissolved LiPSs, while the NiS2/Ni2P heterointerface facilitates rapid electron transfer, thereby enhancing the catalytic activity toward LiPSs. The synergistic effect of vacancy engineering and heterointerface coupling further optimizes the local electronic structure of Ni atoms and the interfacial charge distribution. Furthermore, in situ XRD measurements and theoretical calculations confirm that the sulfur-vacancy-rich NiS2/Ni2P heterostructure significantly accelerates the conversion kinetics of LiPSs. Benefiting from this hierarchical structural design, the coating-modified separator effectively suppresses the LiPSs shuttle effect and significantly improves the reversible conversion and cycling stability of Li–S batteries. As a result, the modified cell delivers a reversible capacity of 779 mAh g–1 at 3C, and even under a high sulfur loading of 6.1 mg cm–2, the cell maintains 509 mAh g–1 after 100 cycles at 0.2C, corresponding to an average capacity decay of only 0.0265% per cycle. This work provides a new strategy for designing functionalized separators and offers both theoretical and experimental guidance for the practical development of high-performance Li–S batteries.
{"title":"Sulfur-Vacancy-Rich NiS2/Ni2P Heterostructure Catalyst for Coated Separator Modification to Accelerate Polysulfide Conversion Kinetics in Lithium–Sulfur Batteries","authors":"Jun Zhao, Fei Liu, Hao Wen, Yuantong Liu, Shangyan Zhou, Chunliang Yang, Haijiao Xie, Lin Yang","doi":"10.1021/acssuschemeng.5c12046","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12046","url":null,"abstract":"Lithium–sulfur (Li–S) batteries are regarded as one of the most promising next-generation energy storage systems owing to their high specific energy and environmental friendliness. However, their practical application is still hindered by the Lithium polysulfides (LiPSs) shuttle effect and sluggish reaction kinetics. In this work, a sulfur-vacancy-rich NiS<sub>2</sub>/Ni<sub>2</sub>P heterostructure catalyst was constructed through a combined hydrothermal and vapor phosphorization process and employed to functionalize the separator surface. The sulfur vacancies act as strong adsorption centers that effectively anchor dissolved LiPSs, while the NiS<sub>2</sub>/Ni<sub>2</sub>P heterointerface facilitates rapid electron transfer, thereby enhancing the catalytic activity toward LiPSs. The synergistic effect of vacancy engineering and heterointerface coupling further optimizes the local electronic structure of Ni atoms and the interfacial charge distribution. Furthermore, in situ XRD measurements and theoretical calculations confirm that the sulfur-vacancy-rich NiS<sub>2</sub>/Ni<sub>2</sub>P heterostructure significantly accelerates the conversion kinetics of LiPSs. Benefiting from this hierarchical structural design, the coating-modified separator effectively suppresses the LiPSs shuttle effect and significantly improves the reversible conversion and cycling stability of Li–S batteries. As a result, the modified cell delivers a reversible capacity of 779 mAh g<sup>–1</sup> at 3C, and even under a high sulfur loading of 6.1 mg cm<sup>–2</sup>, the cell maintains 509 mAh g<sup>–1</sup> after 100 cycles at 0.2C, corresponding to an average capacity decay of only 0.0265% per cycle. This work provides a new strategy for designing functionalized separators and offers both theoretical and experimental guidance for the practical development of high-performance Li–S batteries.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129696","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 : 2026-02-05DOI: 10.1021/acssuschemeng.5c12972
Jingjing Li, Biao Feng, Bingrui Wang, Siqi Li, Miao Shi, Hongying Wu, Suxia Ma, Dan Wang
To address the environmental threat of fluorinated gases, blended refrigerants can balance the environmental benefits of low GWP refrigerants with their inherent flammability. Therefore, this study tested the combustion characteristics of HFO-1216/HFC-161 and HFO-1216/HFC-32, and analyzed the products generated during their oxidative pyrolysis. The results indicate that, as the HFO-1216 proportion increases, the flammability range and maximum explosion pressure of HFC-161 first expand and then decrease, while the corresponding parameters for HFC-32 continue to decline. The higher the proportion of HFO-1216, the lower the peak rate of maximum pressure rise of HFC-32 and HFC-161. Then, as the proportion of HFO-1216 increases, changes in toxic products CO, HF, and COF2, as well as the amount of environmentally impactful CO2, were analyzed. The efficiency of HFO-1216/HFC-161 carbon atoms converting into CO and CO2 first increases and then decreases, whereas in HFO-1216/HFC-32, it uninterruptedly decreases. Finally, as the temperature rises, the generation rates of toxic products HF, CO, and COF2 from the two mixed working fluids increase. Compared to HFO-1216/HFC-32, HFO-1216/HFC-161 generates more toxic products. This study provides a new perspective for analyzing the combustion characteristics of HFOs/HFCs.
{"title":"Green Engineering of Low-GWP Refrigerant Blends: Risk Assessment and Product Characteristics","authors":"Jingjing Li, Biao Feng, Bingrui Wang, Siqi Li, Miao Shi, Hongying Wu, Suxia Ma, Dan Wang","doi":"10.1021/acssuschemeng.5c12972","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12972","url":null,"abstract":"To address the environmental threat of fluorinated gases, blended refrigerants can balance the environmental benefits of low GWP refrigerants with their inherent flammability. Therefore, this study tested the combustion characteristics of HFO-1216/HFC-161 and HFO-1216/HFC-32, and analyzed the products generated during their oxidative pyrolysis. The results indicate that, as the HFO-1216 proportion increases, the flammability range and maximum explosion pressure of HFC-161 first expand and then decrease, while the corresponding parameters for HFC-32 continue to decline. The higher the proportion of HFO-1216, the lower the peak rate of maximum pressure rise of HFC-32 and HFC-161. Then, as the proportion of HFO-1216 increases, changes in toxic products CO, HF, and COF<sub>2</sub>, as well as the amount of environmentally impactful CO<sub>2</sub>, were analyzed. The efficiency of HFO-1216/HFC-161 carbon atoms converting into CO and CO<sub>2</sub> first increases and then decreases, whereas in HFO-1216/HFC-32, it uninterruptedly decreases. Finally, as the temperature rises, the generation rates of toxic products HF, CO, and COF<sub>2</sub> from the two mixed working fluids increase. Compared to HFO-1216/HFC-32, HFO-1216/HFC-161 generates more toxic products. This study provides a new perspective for analyzing the combustion characteristics of HFOs/HFCs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"301 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116270","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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