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}
Pub Date : 2026-02-09DOI: 10.1021/acssuschemeng.5c14243
João Matias, Thomas Rodrigues, Cristiana A. V. Torres, Susana Marques, Belina Ribeiro, Francisco Gírio, Maria A. M. Reis, Filomena Freitas
This study integrates the valorization of a lignocellulose material into poly(3-hydroxybutyrate), P(3HB), with biopolymer extraction from bacterial cells with the enzyme alcalase. The work focused on Burkholderia thailandensis DSM 13276 as the P(3HB) producer and on eucalyptus bark, a byproduct from the pulp industry, as the sole feedstock for bacterial cultivation. The eucalyptus bark was hydrolyzed by a cellulolytic enzymatic cocktail following steam explosion and further subjected to ultrafiltration for enzyme recovery. The resulting hydrolysate supported good cell growth, achieving a cell dry weight of 7.67 ± 0.16 g/L within 72 h of cultivation, and high P(3HB) content (60.0 ± 2.19 wt %) in the bacterial cells, clearly favoring biopolymer synthesis over cell growth, as demonstrated by the polymer and growth yields (0.190 gP(3HB)/gsugar and 0.026 gX/gsugar, respectively). High extraction efficiency (96%) and biopolymer purity (100 ± 3.38%) were reached by enzymatic treatment, resulting in a sample with properties aligned with those of commercial P(3HB) in terms of molecular mass distribution, crystallinity, and thermal properties. These findings demonstrate the successful use of a sustainable feedstock together with the application of environmentally friendly technologies based on the use of enzymes for both lignocellulosic saccharification and biopolymer recovery to develop high-quality bioplastics, advancing the goals of a circular bioeconomy.
{"title":"Sustainable Production of Poly(3-hydroxybutyrate) Using Eucalyptus Bark: Integration with Green Downstream Processing","authors":"João Matias, Thomas Rodrigues, Cristiana A. V. Torres, Susana Marques, Belina Ribeiro, Francisco Gírio, Maria A. M. Reis, Filomena Freitas","doi":"10.1021/acssuschemeng.5c14243","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c14243","url":null,"abstract":"This study integrates the valorization of a lignocellulose material into poly(3-hydroxybutyrate), P(3HB), with biopolymer extraction from bacterial cells with the enzyme alcalase. The work focused on <i>Burkholderia thailandensis</i> DSM 13276 as the P(3HB) producer and on eucalyptus bark, a byproduct from the pulp industry, as the sole feedstock for bacterial cultivation. The eucalyptus bark was hydrolyzed by a cellulolytic enzymatic cocktail following steam explosion and further subjected to ultrafiltration for enzyme recovery. The resulting hydrolysate supported good cell growth, achieving a cell dry weight of 7.67 ± 0.16 g/L within 72 h of cultivation, and high P(3HB) content (60.0 ± 2.19 wt %) in the bacterial cells, clearly favoring biopolymer synthesis over cell growth, as demonstrated by the polymer and growth yields (0.190 g<sub>P(3HB)</sub>/g<sub>sugar</sub> and 0.026 g<sub>X</sub>/g<sub>sugar</sub>, respectively). High extraction efficiency (96%) and biopolymer purity (100 ± 3.38%) were reached by enzymatic treatment, resulting in a sample with properties aligned with those of commercial P(3HB) in terms of molecular mass distribution, crystallinity, and thermal properties. These findings demonstrate the successful use of a sustainable feedstock together with the application of environmentally friendly technologies based on the use of enzymes for both lignocellulosic saccharification and biopolymer recovery to develop high-quality bioplastics, advancing the goals of a circular bioeconomy.","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":"146146273","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}
As a promising high-performance anode, silicon (Si) has a high theoretical specific capacity and low working voltage; however, its substantial volume expansion during lithiation would heavily disrupt electron and ion pathways within the electrode, ultimately causing capacity degradation. Herein, inspired by the “facilitated diffusion through ion channels” mode of biological cellular material in the cell membrane, a novel aqueous binder of binary-metal-engineered alginate-Prussian blue analogs (Alg-PBAs) via a sequential coprecipitation reaction is proposed. The ionic conductivity (1.718 × 10–4 S cm–1) and adhesion strength (4.71 N cm–1) of the Alg-PBA binder are significantly improved by controlling the distribution of metal ions and PBA crystals. The obtained Alg-PBA binder with a highly conductive network and rich polar groups (−OH, −C═O, −C≡N) could not only form a uniform conductive nanolayer on the surface of Si particles but also establish an integrated structure within Si particles and the current collector. As a result, the designed Alg-PBA binder enables the Si anode with a relatively low overall resistance, an enhanced capacity retention even at a high mass loading of 2.2 mg cm–2, and a diminished polarization at a high current density of 2.1 A g–1. These results provide a promising pathway for the development of high-energy-density Si-based lithium-ion batteries.
硅（Si）具有较高的理论比容量和较低的工作电压，是一种很有前途的高性能阳极；然而，它在锂化过程中的大量体积膨胀会严重破坏电极内的电子和离子通路，最终导致容量下降。在此，受生物细胞材料在细胞膜中“通过离子通道促进扩散”模式的启发，提出了一种通过顺序共沉淀反应的新型双金属工程海藻酸盐-普鲁士蓝类似物（Alg-PBAs）的水性粘合剂。通过控制金属离子和PBA晶体的分布，可以显著提高Alg-PBA粘结剂的离子电导率（1.718 × 10-4 S cm-1）和粘附强度（4.71 N cm-1）。所制得的具有高导电性网络和丰富极性基团（−OH,−C = O,−C≡N）的Alg-PBA粘结剂不仅可以在Si颗粒表面形成均匀的导电纳米层，而且可以在Si颗粒和集流器内部建立集成结构。因此，设计的Alg-PBA粘结剂使Si阳极具有相对较低的总电阻，即使在2.2 mg cm-2的高质量负载下也能增强容量保持，并且在2.1 a g-1的高电流密度下也能减弱极化。这些结果为高能量密度硅基锂离子电池的发展提供了一条有希望的途径。
{"title":"Binary-Metal-Engineered Aqueous Binder with Enhanced Ionic Conductivity and Adhesion Strength for Silicon Anodes","authors":"Fengheng Li, Jiarun Liu, Xiaoheng He, Hong Pan, Yifan Wang, Yong Xiang, Hao Wang, Fei Li, Fang Wu","doi":"10.1021/acssuschemeng.5c11127","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11127","url":null,"abstract":"As a promising high-performance anode, silicon (Si) has a high theoretical specific capacity and low working voltage; however, its substantial volume expansion during lithiation would heavily disrupt electron and ion pathways within the electrode, ultimately causing capacity degradation. Herein, inspired by the “facilitated diffusion through ion channels” mode of biological cellular material in the cell membrane, a novel aqueous binder of binary-metal-engineered alginate-Prussian blue analogs (Alg-PBAs) via a sequential coprecipitation reaction is proposed. The ionic conductivity (1.718 × 10<sup>–4</sup> S cm<sup>–1</sup>) and adhesion strength (4.71 N cm<sup>–1</sup>) of the Alg-PBA binder are significantly improved by controlling the distribution of metal ions and PBA crystals. The obtained Alg-PBA binder with a highly conductive network and rich polar groups (−OH, −C═O, −C≡N) could not only form a uniform conductive nanolayer on the surface of Si particles but also establish an integrated structure within Si particles and the current collector. As a result, the designed Alg-PBA binder enables the Si anode with a relatively low overall resistance, an enhanced capacity retention even at a high mass loading of 2.2 mg cm<sup>–2</sup>, and a diminished polarization at a high current density of 2.1 A g<sup>–1</sup>. These results provide a promising pathway for the development of high-energy-density Si-based lithium-ion batteries.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146459","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.
具有较高理论比容量的NH4V4O10在重复的Zn2+ (de)插层过程中由于不可逆的脱脱和结构的不稳定性，限制了其应用。以往的研究主要是利用过量的非活性金属离子预插部分替代NH4+离子，提高了循环稳定性，但以降低可逆比容量为代价。本文合成了一种低含量的Mg2+预插NH4V4O10 (MNVO, Mg:V = 0.036:4)，不取代层间NH4+离子，实现了结构稳定，实现了高稳定性的锌离子存储。表征结果表明，低含量Mg2+的预插层诱导了良好的形态和结构效应。MNVO具有由卷曲纳米片构成的三维分层球形结构，可以促进均匀的应力分布，并有效减轻长时间Zn2+ (de)插层循环过程中的结构退化。更重要的是，非原位XRD和XPS结果表明，低含量的Mg2+预插层从根本上抑制了MNVO中不可逆脱氨和副产物形成的双重降解途径，从而保持了结构的完整性。得益于这些优势，MNVO在低电流密度（0.5 A g-1下500次循环后94%）和高电流密度（5 A g-1下5000次循环后94%）下都实现了出色的容量保持。这种低含量阳离子预插策略为开发高稳定性的层状钒基水性锌离子电池正极材料提供了新的思路。
{"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 : 2026-02-09DOI: 10.1021/acssuschemeng.5c12683
Kai Qi Tan, Duanxing Li, Siew Chun Low, Shinya Furukawa
The energy-intensive nature of the catalytic pyrolysis of plastic for fuel production remains a major challenge in the renewable energy field. To address this, the feed-catalyst bed of a vertical tubular pyrolysis reactor was optimized to upcycle polyethylene (PE) into fuel-range hydrocarbons. Using a dual-stage feed-catalyst bed design (feed-to-catalyst ratio of 5:1), 86.1 wt % conversion of PE was achieved at 300 °C. Compared to the single-stage design, this design improved conversion by 1.68-fold, attributed to the sequential cracking effect. This effect was amplified when a set of zeolites with a 12-membered ring (faujasite and mordenite) was incorporated, achieving a gasoline selectivity of 55.9%. The enhanced performance demonstrates that the dual-stage catalyst bed offers a promising design strategy for enabling low-temperature plastic upcycling with potential applications in renewable carbon resources.
{"title":"Low-Temperature Upcycling of Polyethylene into Fuel-Range Hydrocarbons: An Innovative Approach on the Feed-Catalyst Bed Design","authors":"Kai Qi Tan, Duanxing Li, Siew Chun Low, Shinya Furukawa","doi":"10.1021/acssuschemeng.5c12683","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12683","url":null,"abstract":"The energy-intensive nature of the catalytic pyrolysis of plastic for fuel production remains a major challenge in the renewable energy field. To address this, the feed-catalyst bed of a vertical tubular pyrolysis reactor was optimized to upcycle polyethylene (PE) into fuel-range hydrocarbons. Using a dual-stage feed-catalyst bed design (feed-to-catalyst ratio of 5:1), 86.1 wt % conversion of PE was achieved at 300 °C. Compared to the single-stage design, this design improved conversion by 1.68-fold, attributed to the sequential cracking effect. This effect was amplified when a set of zeolites with a 12-membered ring (faujasite and mordenite) was incorporated, achieving a gasoline selectivity of 55.9%. The enhanced performance demonstrates that the dual-stage catalyst bed offers a promising design strategy for enabling low-temperature plastic upcycling with potential applications in renewable carbon resources.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"108 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146274","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.
我们提出了由Pt2FeCu/C三元合金衍生的有序六边形环形纳米板（O-HDP）的创建和评估，该纳米板可作为聚合物电解质膜燃料电池（pemfc）中氧还原反应（ORR）的高效阴极催化剂。该催化剂采用无表面活性剂熔盐技术制备，并通过x射线衍射（XRD）和透射电子显微镜（TEM）分析证实其具有独特的甜甜圈形状的有序面心四方晶格。电化学测试表明，与Pt/C相比，活性增加了近17倍，同时保持高达50k电位循环的稳定性。在H2/O2条件下的单电池PEMFC评估中，O-HDP Pt2FeCu/C在电流密度为3.98 a cm-2时达到了1.711 W cm-2的峰值功率密度，并在30000次耐久性循环后保持了91%的最大性能。优异的活性和长期稳定性归功于其有序的原子结构、减小的Pt-Pt间距、独特的结构几何形状和协同合金效应，使其成为未来PEMFC应用的有希望的候选者。此外，利用Matlab/Simscape在城市动力计驱动计划（UDDS）驱动循环下对PEMFC堆栈进行了仿真，成功地复制了真实的动态电压（380-500 V）、功率（55-60 kW）和热响应，证实了该模型作为不可用硬件的替代品的有效性。相互关联的电化学和热行为突出了热管理对于保持汽车条件变化时堆叠效率和寿命的重要性。
{"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.
以二氧化碳为唯一碳源合成氨基酸是可持续生物制造的关键目标，为受温室气体排放和资源竞争困扰的传统生产方法提供了一种绿色替代方案。在这里，我们构建了一个高效的无细胞酶平台，用于从二氧化碳中直接生物合成天冬氨酸。我们的集成平台将一个碳固定模块与一个定制设计的合成级联结合起来，该级联使用修饰的还原甘氨酸途径（rGlyP）将两个甘氨酸分子凝聚成天冬氨酸，由甘氨酸氧化酶和重新设计的b-羟基天冬氨酸循环（BHAC）驱动。这个多酶系统的一个关键挑战是实现途径协同。为了解决这个问题，我们采用酶约束静态模型来合理设计五酶级联的最佳化学计量。这种计算方法不仅使最终的天冬氨酸产量提高了25%以上，而且对于确定甘氨酸氧化酶（Bs-ThiO）是主要的速率限制瓶颈至关重要。通过对酶、反应条件和投料策略的系统优化，该体系最终在2 h内积累了17.3 mM （2.3 g/L）的天冬氨酸，达到了模型预测理论产量的92%。该研究为绿色氨基酸生产建立了一个强大且可持续的平台，并展示了将计算设计与无细胞工程相结合的巨大潜力，以推进基于二氧化碳的生物制造的前沿。
{"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.
锂硫电池（li -硫电池）因其高比能和环境友好性被认为是最有前途的下一代储能系统之一。然而，它们的实际应用仍然受到多硫化锂（LiPSs）穿梭效应和反应动力学缓慢的阻碍。本研究通过水热和蒸汽相结合的方法，构建了一种富硫空位的NiS2/Ni2P异质结构催化剂，并将其用于分离器表面的功能化。硫空位作为强吸附中心，有效锚定溶解的LiPSs，而NiS2/Ni2P异质界面促进了快速的电子转移，从而增强了对LiPSs的催化活性。空位工程和异质界面耦合的协同效应进一步优化了Ni原子的局域电子结构和界面电荷分布。此外，原位XRD测量和理论计算证实，富含硫空位的NiS2/Ni2P异质结构显著加速了LiPSs的转化动力学。得益于这种分层结构设计，涂层改性隔膜有效抑制了lips的穿梭效应，显著提高了Li-S电池的可逆转换和循环稳定性。结果表明，改进后的电池在3C时提供了779 mAh g-1的可逆容量，即使在6.1 mg cm-2的高硫负荷下，电池在0.2C下循环100次后仍保持509 mAh g-1，对应于每个循环的平均容量衰减仅为0.0265%。本研究为功能化隔膜的设计提供了新的思路，为高性能锂电池的实际开发提供了理论和实验指导。
{"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}
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