Pub Date : 2026-03-17DOI: 10.1021/acssuschemeng.5c12302
Michael S. Behrendt, Brandon D. Howard, Daniel Holmes, Scott Calabrese Barton, John R. Dorgan
The long sought-after goal of chemically recycling polyolefins at ambient temperature and pressure without the use of organic solvents is realized. Using ozone to regenerate a permanganate oxidant in situ in an aqueous environment, low-density polyethylene is converted to carboxylic acids and oligomeric wax. LDPE powder (with average particle sizes between 150 and 250 μm) serves as the substrate─reactions are conducted at atmospheric pressure and 30 °C. Water-soluble products are quantified using HPLC, with diacids having 4, 5, and 6 carbon units as the primary products. The remaining solid wax was analyzed for crystallinity by calorimetry (DSC), for acid number by titration, and for molecular functionality by ATR-IR and NMR spectroscopies. All three measured quantities increase with increasing reaction time. The acid number of the residual wax indicates a diacid carbon length of ∼30 (∼450 g/mol). Polymer oxidation occurs preferentially at side-chain branch points. Results suggest a two-reaction system in which branch-point tertiary carbons are selectively oxidized to yield linear carboxylic acids and ketones, followed by secondary depolymerization to yield water-soluble diacids. Experimental yields were 10% at 144 h.
{"title":"Aqueous Depolymerization of Polyethylene at Ambient Temperature: In Situ Generation of Permanganate Using Ozone","authors":"Michael S. Behrendt, Brandon D. Howard, Daniel Holmes, Scott Calabrese Barton, John R. Dorgan","doi":"10.1021/acssuschemeng.5c12302","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12302","url":null,"abstract":"The long sought-after goal of chemically recycling polyolefins at ambient temperature and pressure without the use of organic solvents is realized. Using ozone to regenerate a permanganate oxidant <i>in situ</i> in an aqueous environment, low-density polyethylene is converted to carboxylic acids and oligomeric wax. LDPE powder (with average particle sizes between 150 and 250 μm) serves as the substrate─reactions are conducted at atmospheric pressure and 30 °C. Water-soluble products are quantified using HPLC, with diacids having 4, 5, and 6 carbon units as the primary products. The remaining solid wax was analyzed for crystallinity by calorimetry (DSC), for acid number by titration, and for molecular functionality by ATR-IR and NMR spectroscopies. All three measured quantities increase with increasing reaction time. The acid number of the residual wax indicates a diacid carbon length of ∼30 (∼450 g/mol). Polymer oxidation occurs preferentially at side-chain branch points. Results suggest a two-reaction system in which branch-point tertiary carbons are selectively oxidized to yield linear carboxylic acids and ketones, followed by secondary depolymerization to yield water-soluble diacids. Experimental yields were 10% at 144 h.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"87 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465995","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 : 2026-03-16DOI: 10.1021/acssuschemeng.5c12682
Zhaowei Ren, Xiaoli Hu, Muhammad Imran Anwar, Hui Hu, Jianyi Wang, Xiaofang Su, Jingyi Wu, Songtao Xiao, Yanan Gao
Aqueous zinc−iodine (Zn−I2) batteries demonstrate promising potential for large−scale energy storage applications. However, the uncontrolled “shuttle effect” of polyiodides (I3−, I5−) results in capacity loss, lower Coulombic efficiency (CE), and poor cycling reversibility. Herein, we propose alkyne−rich covalent organic frameworks (COFs) as functional separator coatings to effectively suppress the “shuttle effect”, establishing a protective solid electrolyte interphase (SEI) layer to stabilize the Zn metal anode. The effect of different alkyne contents in COFs on the performance of Zn−I2 batteries is investigated, and the results demonstrate that increasing alkyne content significantly improves CE, ion migration rate, and cycling stability. Remarkably, the 100% alkyne−functionalized TAPT−BPTA−COF separator exhibited excellent ion selectivity, effectively blocking the diffusion of polyiodide species, while favoring the transport of Zn2+. This selective transport ensures uniform deposition of Zn2+ on the anode during cycles, thereby reducing internal resistance and improving cycle performance. Notably, the Zn||TAPT−BPTA−COF||I2 battery delivers an initial capacity of 8.4 mAh cm−2 at 20 mA cm−2, retaining 70.1% of the initial capacity over 1200 cycles with 99% CE. Complementary spectroscopic analyses and visualization experiments further confirm that the fully alkyne−conjugated electronic structure of COFs enhances electrical conductivity. This study provides a molecular design strategy for developing high−performance, COF−based electrochemical materials for Zn−I2 battery systems.
锌-碘（Zn - I2）水性电池在大规模储能应用中具有广阔的潜力。然而，多碘化物（I3−,I5−）不受控制的“穿梭效应”导致容量损失，库仑效率（CE）降低，循环可逆性差。在此，我们提出了富炔-共价有机框架（COFs）作为功能隔膜涂层，以有效抑制“穿梭效应”，建立一个保护固体电解质界面（SEI）层来稳定Zn金属阳极。研究了COFs中不同炔烃含量对Zn−I2电池性能的影响，结果表明，增加炔烃含量可显著提高电池的CE、离子迁移率和循环稳定性。值得注意的是，100%炔功能化的tpt - BPTA - COF分离器表现出优异的离子选择性，有效地阻止了多碘化物的扩散，同时有利于Zn2+的运输。这种选择性输运确保了Zn2+在循环过程中均匀沉积在阳极上，从而降低了内阻，提高了循环性能。值得注意的是，Zn|| tpt - BPTA - COF||I2电池在20 mA cm - 2下的初始容量为8.4 mAh cm - 2，在1200次循环中保持了70.1%的初始容量，CE为99%。互补光谱分析和可视化实验进一步证实了COFs的全炔共轭电子结构增强了其导电性。本研究提供了一种分子设计策略，用于开发高性能、基于COF的锌离子电池系统电化学材料。
{"title":"Alkyne−Functionalized Covalent Organic Frameworks for Suppressing Polyiodide Shuttle Effect in Aqueous Zinc−Iodine Batteries","authors":"Zhaowei Ren, Xiaoli Hu, Muhammad Imran Anwar, Hui Hu, Jianyi Wang, Xiaofang Su, Jingyi Wu, Songtao Xiao, Yanan Gao","doi":"10.1021/acssuschemeng.5c12682","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12682","url":null,"abstract":"Aqueous zinc−iodine (Zn−I<sub>2</sub>) batteries demonstrate promising potential for large−scale energy storage applications. However, the uncontrolled “shuttle effect” of polyiodides (I<sub>3</sub><sup>−</sup>, I<sub>5</sub><sup>−</sup>) results in capacity loss, lower Coulombic efficiency (CE), and poor cycling reversibility. Herein, we propose alkyne−rich covalent organic frameworks (COFs) as functional separator coatings to effectively suppress the “shuttle effect”, establishing a protective solid electrolyte interphase (SEI) layer to stabilize the Zn metal anode. The effect of different alkyne contents in COFs on the performance of Zn−I<sub>2</sub> batteries is investigated, and the results demonstrate that increasing alkyne content significantly improves CE, ion migration rate, and cycling stability. Remarkably, the 100% alkyne−functionalized TAPT−BPTA−COF separator exhibited excellent ion selectivity, effectively blocking the diffusion of polyiodide species, while favoring the transport of Zn<sup>2+</sup>. This selective transport ensures uniform deposition of Zn<sup>2+</sup> on the anode during cycles, thereby reducing internal resistance and improving cycle performance. Notably, the Zn||TAPT−BPTA−COF||I<sub>2</sub> battery delivers an initial capacity of 8.4 mAh cm<sup>−2</sup> at 20 mA cm<sup>−2</sup>, retaining 70.1% of the initial capacity over 1200 cycles with 99% CE. Complementary spectroscopic analyses and visualization experiments further confirm that the fully alkyne−conjugated electronic structure of COFs enhances electrical conductivity. This study provides a molecular design strategy for developing high−performance, COF−based electrochemical materials for Zn−I<sub>2</sub> battery systems.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462091","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 : 2026-03-16DOI: 10.1021/acssuschemeng.5c13790
Xiaoxiong Li,Yuan Li,Zhonghai Fang,Ranran Dai,Mengjie Niu,Zhaohui Xiao,Shiwei Lin
Electrocatalytic hydrogenation (ECH) offers a sustainable route for chemical production under ambient conditions; however, it faces challenges including intense competition from the hydrogen evolution reaction (HER) and reliance on precious metal-based electrocatalysts. Herein, we report, for the first time, the integration of molybdenum disulfide (MoS2) with defect engineering to develop highly efficient, noble-metal-free electrocatalysts. This defect control strategy effectively modulates the electronic structure and increases the specific surface area, thereby promoting the ECH of biomass-derived oxygenates while suppressing H2 evolution. Defect-rich molybdenum disulfide nanosheets (denoted as D-MoS2) successfully catalyze the hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF). At a potential of −0.2 V (vs RHE), D-MoS2 achieves a Faradaic efficiency (FE) of 93% for BHMF, a production rate of 0.69 mmol·cm–2·h–1, and a conversion of 72%, while the FE for H2 remains as low as 8%. The BHMF production rate reaches a maximum of 0.85 mmol·cm–2·h–1 at −0.3 V (vs RHE). These superior performances are attributed to enhanced chemical adsorption and an increased specific surface area. Specifically, the adsorption of H* intermediates and HMF molecules at the edge sites of D-MoS2 is synergistically strengthened, accelerating the surface reaction steps following the Langmuir–Hinshelwood mechanism. This work opens up new avenues for the design of advanced electrocatalysts for electrochemical synthesis applications.
电催化加氢（ECH）为环境条件下的化工生产提供了一条可持续的途径；然而，它面临着来自析氢反应（HER）的激烈竞争和对贵金属基电催化剂的依赖等挑战。本文首次报道了将二硫化钼（MoS2）与缺陷工程相结合，开发出高效、无贵金属的电催化剂。这种缺陷控制策略有效地调节了电子结构，增加了比表面积，从而促进了生物质衍生氧合物的ECH，同时抑制了H2的析出。富缺陷二硫化钼纳米片（D-MoS2）成功催化5-羟甲基糠醛（HMF）加氢生成2,5-二（羟甲基）呋喃（BHMF）。在−0.2 V （vs RHE）电位下，D-MoS2对BHMF的法拉第效率（FE）为93%，产率为0.69 mmol·cm-2·h-1，转化率为72%，而H2的FE仍低至8%。在−0.3 V （vs RHE）下BHMF的产率最高，为0.85 mmol·cm-2·h-1。这些优越的性能归因于增强的化学吸附和增加的比表面积。具体来说，H*中间体和HMF分子在D-MoS2边缘位置的吸附被协同加强，加速了表面反应步骤，遵循Langmuir-Hinshelwood机制。这项工作为设计用于电化学合成的先进电催化剂开辟了新的途径。
{"title":"Defect Engineering Modulates the Edge Microenvironment of MoS2 for Significantly Enhanced Selective Electrocatalytic Hydrogenation of 5-Hydroxymethylfurfural","authors":"Xiaoxiong Li,Yuan Li,Zhonghai Fang,Ranran Dai,Mengjie Niu,Zhaohui Xiao,Shiwei Lin","doi":"10.1021/acssuschemeng.5c13790","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13790","url":null,"abstract":"Electrocatalytic hydrogenation (ECH) offers a sustainable route for chemical production under ambient conditions; however, it faces challenges including intense competition from the hydrogen evolution reaction (HER) and reliance on precious metal-based electrocatalysts. Herein, we report, for the first time, the integration of molybdenum disulfide (MoS2) with defect engineering to develop highly efficient, noble-metal-free electrocatalysts. This defect control strategy effectively modulates the electronic structure and increases the specific surface area, thereby promoting the ECH of biomass-derived oxygenates while suppressing H2 evolution. Defect-rich molybdenum disulfide nanosheets (denoted as D-MoS2) successfully catalyze the hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF). At a potential of −0.2 V (vs RHE), D-MoS2 achieves a Faradaic efficiency (FE) of 93% for BHMF, a production rate of 0.69 mmol·cm–2·h–1, and a conversion of 72%, while the FE for H2 remains as low as 8%. The BHMF production rate reaches a maximum of 0.85 mmol·cm–2·h–1 at −0.3 V (vs RHE). These superior performances are attributed to enhanced chemical adsorption and an increased specific surface area. Specifically, the adsorption of H* intermediates and HMF molecules at the edge sites of D-MoS2 is synergistically strengthened, accelerating the surface reaction steps following the Langmuir–Hinshelwood mechanism. This work opens up new avenues for the design of advanced electrocatalysts for electrochemical synthesis applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lignin pyrolysis exhibits limited yield and selectivity of monophenols, primarily due to the formation of undesirable phenolic oligomers. Previous studies predominantly focused on oligomers derived from the incomplete depolymerization of lignin macromolecules, while the contribution of monomer repolymerization to oligomers remains poorly understood. To address this knowledge gap, this study introduces the first-time application of vacuum ultraviolet photoionization aerosol mass spectrometry (VUV-PI-AMS) for real-time tracking of the dimerization dynamics of lignin model monomers (guaiacol and syringol) during fast pyrolysis. By directly analyzing aerosol-phase products, our work reveals critical mechanistic insights. Results demonstrate that elevated pyrolysis temperatures and prolonged residence times significantly enhance both the diversity and the extent of dimer formation. Notably, syringol generates heavier and structurally more complex dimers than guaiacol, highlighting the role of methoxy groups in radical–radical coupling reactions. Complementary offline analyses (ESI-HRMS and GC-MS) further corroborate the prevalence of biphenyl-core structures linked via ether, ketone, or direct C–C bonds. These findings elucidate distinct radical-initiated pathways for monomer repolymerization in lignin pyrolysis, confirming its important role in phenolic oligomer formation. The mechanistic insights from this aerosol-focused study guide the development of future strategies to suppress oligomer formation and enhance monophenol yields.
{"title":"Mechanistic Insights into Lignin-Monomer Repolymerization in Fast Pyrolysis via Aerosol Product Analysis","authors":"Liangyuan Jia,Yi Shao,Ruibin Yuan,Zuoying Wen,Peiqi Liu,Hualin Wang,Zhongyue Zhou,Cunyong Zhang,Shaolin Ge,Xiaofeng Tang","doi":"10.1021/acssuschemeng.6c01869","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c01869","url":null,"abstract":"Lignin pyrolysis exhibits limited yield and selectivity of monophenols, primarily due to the formation of undesirable phenolic oligomers. Previous studies predominantly focused on oligomers derived from the incomplete depolymerization of lignin macromolecules, while the contribution of monomer repolymerization to oligomers remains poorly understood. To address this knowledge gap, this study introduces the first-time application of vacuum ultraviolet photoionization aerosol mass spectrometry (VUV-PI-AMS) for real-time tracking of the dimerization dynamics of lignin model monomers (guaiacol and syringol) during fast pyrolysis. By directly analyzing aerosol-phase products, our work reveals critical mechanistic insights. Results demonstrate that elevated pyrolysis temperatures and prolonged residence times significantly enhance both the diversity and the extent of dimer formation. Notably, syringol generates heavier and structurally more complex dimers than guaiacol, highlighting the role of methoxy groups in radical–radical coupling reactions. Complementary offline analyses (ESI-HRMS and GC-MS) further corroborate the prevalence of biphenyl-core structures linked via ether, ketone, or direct C–C bonds. These findings elucidate distinct radical-initiated pathways for monomer repolymerization in lignin pyrolysis, confirming its important role in phenolic oligomer formation. The mechanistic insights from this aerosol-focused study guide the development of future strategies to suppress oligomer formation and enhance monophenol yields.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462243","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}
While biocatalysis in ionic liquids (ILs) using a single enzyme is well known, the successful performance of enzyme cascade reactions (ECRs) using multiple enzymes in ILs is limited by the incompatible stabilization of more than one enzyme in a single IL. Here, we introduce an innovative approach where stoichiometric precision of ILs creates pH-switchable media that dynamically modulate multienzyme microenvironments and maintain the functional integrity of ECR without requiring any proximity-engineered scaffolds. Cholinium-based ILs, with phosphate and carboxylate anions, were synthesized with varying molar ratios of cholinium to realize pH-switchable aqueous platforms for ECR. Using glucose oxidase (GOx)–horseradish peroxidase as (HRP) an enzymatic cascade, we demonstrate that under optimized conditions aqueous solutions of ILs significantly enhance both the individual enzyme (GOx and HRP) activities and ECR (GOx–HRP) efficiencies compared to the control, phosphate-buffered saline (PBS) (pH 7.4). Molecular docking, molecular dynamics simulations, UV–vis, and circular dichroism spectroscopy studies reveal that ILs are involved in soft interactions with enzymes, stabilizing catalytically favorable conformations, and protecting enzymes against thermal-stress. Remarkably, a 25-fold increase in the ECR efficiency was achieved in 10 wt % of [Ch]2[PAA] through [Ch]2[PAA] assisted improved substrate channeling and reduced transition-state energy barriers. Moreover, an ∼16% increase in the half-life temperature (T50) of GOx–HRP cascade in the presence of 10 wt % [Ch]2[PAA] with an enhanced melting temperature (Tm) of the enzymes suggested improved thermal stability relative to PBS. The results of improved enzyme stability in hydrated ILs were further investigated by the thermodynamic stability curves (ΔG vs T). Overall, this work provides a basis for multienzyme biocatalysis in aqueous solution of ILs with an accelerated ECR rate and improved thermodynamic stability, envisaging sustainable biocatalysis and metabolic engineering.
{"title":"Stoichiometrically Engineered Hydrated Ionic Liquids Enabling Reinforcement of Enzyme Cascade with Improved Thermodynamic Stability","authors":"Sagar Biswas, Dheeraj Kumar Sarkar, Aaftaab Sethi, Pranav Bharadwaj, Rakesh Sinha, Pankaj Bharmoria, Gregory Franklin, Dibyendu Mondal","doi":"10.1021/acssuschemeng.5c13384","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13384","url":null,"abstract":"While biocatalysis in ionic liquids (ILs) using a single enzyme is well known, the successful performance of enzyme cascade reactions (ECRs) using multiple enzymes in ILs is limited by the incompatible stabilization of more than one enzyme in a single IL. Here, we introduce an innovative approach where stoichiometric precision of ILs creates pH-switchable media that dynamically modulate multienzyme microenvironments and maintain the functional integrity of ECR without requiring any proximity-engineered scaffolds. Cholinium-based ILs, with phosphate and carboxylate anions, were synthesized with varying molar ratios of cholinium to realize pH-switchable aqueous platforms for ECR. Using glucose oxidase (GOx)–horseradish peroxidase as (HRP) an enzymatic cascade, we demonstrate that under optimized conditions aqueous solutions of ILs significantly enhance both the individual enzyme (GOx and HRP) activities and ECR (GOx–HRP) efficiencies compared to the control, phosphate-buffered saline (PBS) (pH 7.4). Molecular docking, molecular dynamics simulations, UV–vis, and circular dichroism spectroscopy studies reveal that ILs are involved in soft interactions with enzymes, stabilizing catalytically favorable conformations, and protecting enzymes against thermal-stress. Remarkably, a 25-fold increase in the ECR efficiency was achieved in 10 wt % of [Ch]<sub>2</sub>[PAA] through [Ch]<sub>2</sub>[PAA] assisted improved substrate channeling and reduced transition-state energy barriers. Moreover, an ∼16% increase in the half-life temperature (<i>T</i><sub>50</sub>) of GOx–HRP cascade in the presence of 10 wt % [Ch]<sub>2</sub>[PAA] with an enhanced melting temperature (<i>T</i><sub>m</sub>) of the enzymes suggested improved thermal stability relative to PBS. The results of improved enzyme stability in hydrated ILs were further investigated by the thermodynamic stability curves (Δ<i>G</i> vs <i>T</i>). Overall, this work provides a basis for multienzyme biocatalysis in aqueous solution of ILs with an accelerated ECR rate and improved thermodynamic stability, envisaging sustainable biocatalysis and metabolic engineering.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"70 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462093","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 precise design of a high-entropy cathode material can achieve excellent performance. Many scholars have conducted extensive research on element design, but studies on the roles of each element are relatively scarce in high-entropy systems. In this project, we adjusted the composition of Cu/Co elements and developed three materials, NaNi0.25Fe0.15Mn0.3Ti0.1Ce0.02Co0.09Li0.1O2 (HEO-Co), NaNi0.25Fe0.15Mn0.3Ti0.1Ce0.02Cu0.06Co0.05Li0.1O2 (HEO-CC), and NaNi0.25Fe0.15Mn0.3Ti0.1Ce0.02Cu0.13Li0.11O2 (HEO-Cu). The physical properties and electrochemical performances are analyzed. The appropriate introduction of the Cu element can reduce the voltage difference between the redox potential and the electrochemical polarization. Moreover, it possesses outstanding air and structural stability. The appropriate proportion of the Co element can expand the interlayer spacing of the Na layer, increase the diffusion coefficient of Na+, and achieve excellent rate performance. The appropriate ratio of Cu and Co combines the advantages of both elements, endowing cathode materials with a stable structure, excellent air stability, and electrochemical performance. This work thoroughly explores the specific roles of Cu and Co elements, providing valuable insights for the design of high-entropy cathode materials and a practical pathway toward industrial-scale applications.
{"title":"Regulated Cu/Co Elemental Composition To Build High-Performance Cathode Materials of Sodium-Ion Batteries","authors":"Xiangnan Li, Ziya Zhang, Xiaojian Liu, Zhenpu Shi, Kaige Lu, Yanhong Yin, Hongyu Dong, Yange Yang, Baopeng Li, Huishuang Zhang, Shu-Ting Yang","doi":"10.1021/acssuschemeng.5c12729","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12729","url":null,"abstract":"The precise design of a high-entropy cathode material can achieve excellent performance. Many scholars have conducted extensive research on element design, but studies on the roles of each element are relatively scarce in high-entropy systems. In this project, we adjusted the composition of Cu/Co elements and developed three materials, NaNi<sub>0.25</sub>Fe<sub>0.15</sub>Mn<sub>0.3</sub>Ti<sub>0.1</sub>Ce<sub>0.02</sub>Co<sub>0.09</sub>Li<sub>0.1</sub>O<sub>2</sub> (HEO-Co), NaNi<sub>0.25</sub>Fe<sub>0.15</sub>Mn<sub>0.3</sub>Ti<sub>0.1</sub>Ce<sub>0.02</sub>Cu<sub>0.06</sub>Co<sub>0.05</sub>Li<sub>0.1</sub>O<sub>2</sub> (HEO-CC), and NaNi<sub>0.25</sub>Fe<sub>0.15</sub>Mn<sub>0.3</sub>Ti<sub>0.1</sub>Ce<sub>0.02</sub>Cu<sub>0.13</sub>Li<sub>0.11</sub>O<sub>2</sub> (HEO-Cu). The physical properties and electrochemical performances are analyzed. The appropriate introduction of the Cu element can reduce the voltage difference between the redox potential and the electrochemical polarization. Moreover, it possesses outstanding air and structural stability. The appropriate proportion of the Co element can expand the interlayer spacing of the Na layer, increase the diffusion coefficient of Na<sup>+</sup>, and achieve excellent rate performance. The appropriate ratio of Cu and Co combines the advantages of both elements, endowing cathode materials with a stable structure, excellent air stability, and electrochemical performance. This work thoroughly explores the specific roles of Cu and Co elements, providing valuable insights for the design of high-entropy cathode materials and a practical pathway toward industrial-scale applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462094","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}
Metal halide perovskites have been widely utilized in optoelectronic devices due to their exceptional optoelectronic properties. These properties, along with their potential applications, are fundamentally governed by their bandgap and formation energy. In this study, machine learning (ML) was employed as a pivotal approach to efficiently explore A3BX6 perovskites with high stability and promising photoelectric properties. Among the evaluated 12 ML algorithms, the GBR algorithm demonstrated optimal performance and was selected to predict the bandgap and formation energy. Two regression models, namely B_GBR_BOA for bandgap prediction and F_GBR_GA for formation energy prediction, achieved correlation coefficient (R2) scores of 0.986 and 0.992, respectively, while SHapley Additive exPlanations (SHAP) analysis revealed the corresponding critical features. Meanwhile, 461 potential perovskites with bandgaps in the range of 1–4 eV and formation energies lower than −1 eV/atom were screened out from 2,280 virtual candidates. Furthermore, both density functional theory (DFT) calculations and experimental investigations were carried out to verify the promising predictions of ML. The predicted Rb3BiI6 was successfully synthesized and applied in efficient photodetection and photocatalysis for the first time. This work provides a novel strategy for the efficient discovery of lead-free halide perovskites with promising optoelectronic properties and high stability, facilitating the rational design of high-performance optoelectronic devices.
{"title":"Efficient Discovery of Lead-Free A3BX6 Halide Perovskites via Machine Learning","authors":"Xinying Xian, Ding Wang, Ge Xu, Wen Luo, Shenchun Yuan, Feifan Chen, Yayun Pu, Fei Qi, Nan Zhang, Xiaosheng Tang, Qiang Huang","doi":"10.1021/acssuschemeng.5c09606","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09606","url":null,"abstract":"Metal halide perovskites have been widely utilized in optoelectronic devices due to their exceptional optoelectronic properties. These properties, along with their potential applications, are fundamentally governed by their bandgap and formation energy. In this study, machine learning (ML) was employed as a pivotal approach to efficiently explore A<sub>3</sub>BX<sub>6</sub> perovskites with high stability and promising photoelectric properties. Among the evaluated 12 ML algorithms, the GBR algorithm demonstrated optimal performance and was selected to predict the bandgap and formation energy. Two regression models, namely B_GBR_BOA for bandgap prediction and F_GBR_GA for formation energy prediction, achieved correlation coefficient (<i>R</i><sup>2</sup>) scores of 0.986 and 0.992, respectively, while SHapley Additive exPlanations (SHAP) analysis revealed the corresponding critical features. Meanwhile, 461 potential perovskites with bandgaps in the range of 1–4 eV and formation energies lower than −1 eV/atom were screened out from 2,280 virtual candidates. Furthermore, both density functional theory (DFT) calculations and experimental investigations were carried out to verify the promising predictions of ML. The predicted Rb<sub>3</sub>BiI<sub>6</sub> was successfully synthesized and applied in efficient photodetection and photocatalysis for the first time. This work provides a novel strategy for the efficient discovery of lead-free halide perovskites with promising optoelectronic properties and high stability, facilitating the rational design of high-performance optoelectronic devices.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"44 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147447297","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 : 2026-03-14DOI: 10.1021/acssuschemeng.6c00635
Jian Feng, Dongxia Yan, Lingzhi Yu, Xingmei Lu, Jiayu Xin, Junli Xu, Yi Li, Qing Zhou, Ziqing Wang
Biobased 2,5-furandicarboxylic acid (FDCA) is an attractive surrogate for petroleum-derived terephthalic/isophthalic acids, yet its utilization in high-performance polyamides is hindered by monomer instability, end-group deactivation, and the absence of a green synthesis strategy. Herein, a facile controllable sequential copolymerization approach is developed to synthesize furan-based polyamides with balanced mechanical and thermal properties. Specifically, XFX diamine-terminated oligomers were first prepared via an ester–amine exchange reaction in a methanol solution at room temperature (30 °C), using dimethyl 2,5-furandicarboxylate (F) and aliphatic diamine (X) as monomers, and 1-butyl-3-methylimidazolium dihydrogen phosphate ([Bmim][H2PO4]) as the metal-free catalyst. Subsequent melt polycondensation of these oligomers with aliphatic dicarboxylates (Y) afforded a series of furan-based copolyamides (PA(XFX)mY) featuring tailorable sequence structures and tunable balance of strength and toughness. By systematically regulating the alkyl chain lengths of diamines and dicarboxylates, the hydrogen-bond density and segmental rigidity of the copolyamides were precisely tuned, affording copolyamides whose initial decomposition temperature ranges from 329.8 to 386.7 °C and glass-transition temperature ranges from 42.5 to 91.9 °C. At the same time, the copolyamides exhibit a yield strength of 25.80–100.21 MPa and an elongation at break of 56.29–684.61%, performances outperform the corresponding commercial aliphatic polyamides. Molecular dynamics (MD) simulations corroborate that rigid furan rings and robust hydrogen-bond networks cooperate to enhance their thermal and mechanical properties. Overall, this work establishes a viable and sustainable route to high-performance biobased polyamides with tunable functionalities, highlighting their great potential as next-generation engineering plastics and fibers for sustainable materials engineering.
{"title":"Preparation and Properties of High-Strength and High-Toughness Furan-Based Copolyamides PA(XFX)mY via a Facile Sequential Copolymerization Strategy","authors":"Jian Feng, Dongxia Yan, Lingzhi Yu, Xingmei Lu, Jiayu Xin, Junli Xu, Yi Li, Qing Zhou, Ziqing Wang","doi":"10.1021/acssuschemeng.6c00635","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00635","url":null,"abstract":"Biobased 2,5-furandicarboxylic acid (FDCA) is an attractive surrogate for petroleum-derived terephthalic/isophthalic acids, yet its utilization in high-performance polyamides is hindered by monomer instability, end-group deactivation, and the absence of a green synthesis strategy. Herein, a facile controllable sequential copolymerization approach is developed to synthesize furan-based polyamides with balanced mechanical and thermal properties. Specifically, XFX diamine-terminated oligomers were first prepared via an ester–amine exchange reaction in a methanol solution at room temperature (30 °C), using dimethyl 2,5-furandicarboxylate (F) and aliphatic diamine (X) as monomers, and 1-butyl-3-methylimidazolium dihydrogen phosphate ([Bmim][H<sub>2</sub>PO<sub>4</sub>]) as the metal-free catalyst. Subsequent melt polycondensation of these oligomers with aliphatic dicarboxylates (Y) afforded a series of furan-based copolyamides (PA(XFX)<sub><i>m</i></sub>Y) featuring tailorable sequence structures and tunable balance of strength and toughness. By systematically regulating the alkyl chain lengths of diamines and dicarboxylates, the hydrogen-bond density and segmental rigidity of the copolyamides were precisely tuned, affording copolyamides whose initial decomposition temperature ranges from 329.8 to 386.7 °C and glass-transition temperature ranges from 42.5 to 91.9 °C. At the same time, the copolyamides exhibit a yield strength of 25.80–100.21 MPa and an elongation at break of 56.29–684.61%, performances outperform the corresponding commercial aliphatic polyamides. Molecular dynamics (MD) simulations corroborate that rigid furan rings and robust hydrogen-bond networks cooperate to enhance their thermal and mechanical properties. Overall, this work establishes a viable and sustainable route to high-performance biobased polyamides with tunable functionalities, highlighting their great potential as next-generation engineering plastics and fibers for sustainable materials engineering.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147447298","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 : 2026-03-14DOI: 10.1021/acssuschemeng.5c13108
Marco Francesco Torre, Lavanya Veerapuram, Francesco Tavella, Chiara Genovese, Siglinda Perathoner, Federica Torrigino, Pierdomenico Biasi, Gabriele Centi, Claudio Ampelli
Ammonia (NH3) can be synthesized directly from N2 and H2O using plasma micro-discharges formed at the water–electrode interface, offering a promising alternative to both conventional electrocatalysis and nonthermal plasma processes. However, discharge performance and stability are strongly affected by device engineering. This study reports the development and engineering of a hybrid electrochemical device that integrates a micro-plasma cathode for sustainable NH3 production under ambient temperature and pressure. Solvated electrons generated through plasma–liquid interactions, particularly within interfacial aerosol microdroplets, act as highly reducing species, eliminating the need for catalysts or external chemical reagents. The effects of the plasma–liquid gap, gas feed flow rate, discharge current, and cathode inner diameter on NH3 yield are systematically investigated. Optimizing these factors enables Faradaic efficiency exceeding 70% and significantly enhances the instantaneous N2-to-NH3 yield, outperforming previously reported plasma–liquid systems. These findings highlight the importance of system engineering optimization for advancing sustainable plasma-assisted nitrogen fixation and for progressing toward industrial scale-up.
{"title":"Engineering Plasma–Liquid Microdischarge Systems for Direct N2-to-NH3 Conversion at Ambient Conditions","authors":"Marco Francesco Torre, Lavanya Veerapuram, Francesco Tavella, Chiara Genovese, Siglinda Perathoner, Federica Torrigino, Pierdomenico Biasi, Gabriele Centi, Claudio Ampelli","doi":"10.1021/acssuschemeng.5c13108","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13108","url":null,"abstract":"Ammonia (NH<sub>3</sub>) can be synthesized directly from N<sub>2</sub> and H<sub>2</sub>O using plasma <i>micro</i>-discharges formed at the water–electrode interface, offering a promising alternative to both conventional electrocatalysis and nonthermal plasma processes. However, discharge performance and stability are strongly affected by device engineering. This study reports the development and engineering of a hybrid electrochemical device that integrates a <i>micro</i>-plasma cathode for sustainable NH<sub>3</sub> production under ambient temperature and pressure. Solvated electrons generated through plasma–liquid interactions, particularly within interfacial aerosol microdroplets, act as highly reducing species, eliminating the need for catalysts or external chemical reagents. The effects of the plasma–liquid gap, gas feed flow rate, discharge current, and cathode inner diameter on NH<sub>3</sub> yield are systematically investigated. Optimizing these factors enables Faradaic efficiency exceeding 70% and significantly enhances the instantaneous N<sub>2</sub>-to-NH<sub>3</sub> yield, outperforming previously reported plasma–liquid systems. These findings highlight the importance of system engineering optimization for advancing sustainable plasma-assisted nitrogen fixation and for progressing toward industrial scale-up.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147447366","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 : 2026-03-13DOI: 10.1021/acssuschemeng.5c12860
Xunzhen Sun, Xiao Zhang, Hui Gu, Jiayi Li, Fei Lu, Long Su, Xinpei Gao
Aqueous zinc–iodine (Zn–I2) batteries are promising for sustainable energy storage owing to their intrinsic safety, environmental benignity, and the highly reversible redox chemistry of iodine. However, water-induced side reactions at the Zn anode and the shuttling effect of polyiodides trigger severe self-discharge and interfacial instability. Herein, a molecular-weaving–inspired strategy was developed, in which topological chain entanglements cooperate with dynamic ionic/coordination junctions to build a dual-cross-linked hydrogel electrolyte. In such weaving-inspired entangled networks, Zn2+-activated junction dynamics dissipate energy and prevent stress localization, while the enduring entanglement preserves network integrity. Simultaneously, the introduction of abundant coordination sites along the polymer backbone reconfigures the local Zn2+ solvation environment and mitigates Zn anode side reactions and dendrite growth. Moreover, these coordinated Zn2+ nodes effectively suppress the polyiodide shuttle without compromising ionic conductivity. Benefiting from these synergistic effects, the designed hydrogel electrolyte enables highly stable Zn plating/stripping, achieving an average Coulombic efficiency of 99.46% in Zn//Cu cells. The assembled Zn//I2 full cells deliver excellent durability with a high capacity retention of 87.8% after 9000 cycles at 5.0 A g–1. This work establishes a viable weaving-inspired design strategy for natural polymer-based hydrogel electrolytes toward durable aqueous Zn–I2 batteries and beyond.
锌-碘（Zn-I2）水电池由于其固有的安全性、环境友好性和碘的高度可逆氧化还原化学特性，在可持续能源存储方面具有很大的前景。然而，锌阳极的水诱导副反应和多碘化物的穿梭效应会引发严重的自放电和界面不稳定。本文提出了一种受分子编织启发的策略，其中拓扑链纠缠与动态离子/配位结合作构建双交联水凝胶电解质。在这种受编织启发的纠缠网络中，Zn2+激活的结动力学耗散能量并防止应力局部化，而持久的纠缠保持了网络的完整性。同时，在聚合物主链上引入丰富的配位位点，重新配置了局部Zn2+溶剂化环境，减轻了Zn阳极副反应和枝晶生长。此外，这些配位的Zn2+节点有效地抑制了多碘化物穿梭而不影响离子电导率。得益于这些协同效应，所设计的水凝胶电解质能够实现高度稳定的Zn电镀/剥离，在Zn/ Cu电池中实现99.46%的平均库仑效率。组装的Zn/ I2全电池具有优异的耐用性，在5.0 a g-1下循环9000次后容量保持率高达87.8%。这项工作建立了一种可行的编织灵感设计策略，用于天然聚合物基水凝胶电解质，用于耐用的水性锌- i2电池及其他用途。
{"title":"Molecular Weaving-Inspired Dual-Cross-Linked Natural-Polymer Hydrogel Electrolyte for Stable Aqueous Zn–I2 Battery","authors":"Xunzhen Sun, Xiao Zhang, Hui Gu, Jiayi Li, Fei Lu, Long Su, Xinpei Gao","doi":"10.1021/acssuschemeng.5c12860","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12860","url":null,"abstract":"Aqueous zinc–iodine (Zn–I<sub>2</sub>) batteries are promising for sustainable energy storage owing to their intrinsic safety, environmental benignity, and the highly reversible redox chemistry of iodine. However, water-induced side reactions at the Zn anode and the shuttling effect of polyiodides trigger severe self-discharge and interfacial instability. Herein, a molecular-weaving–inspired strategy was developed, in which topological chain entanglements cooperate with dynamic ionic/coordination junctions to build a dual-cross-linked hydrogel electrolyte. In such weaving-inspired entangled networks, Zn<sup>2+</sup>-activated junction dynamics dissipate energy and prevent stress localization, while the enduring entanglement preserves network integrity. Simultaneously, the introduction of abundant coordination sites along the polymer backbone reconfigures the local Zn<sup>2+</sup> solvation environment and mitigates Zn anode side reactions and dendrite growth. Moreover, these coordinated Zn<sup>2+</sup> nodes effectively suppress the polyiodide shuttle without compromising ionic conductivity. Benefiting from these synergistic effects, the designed hydrogel electrolyte enables highly stable Zn plating/stripping, achieving an average Coulombic efficiency of 99.46% in Zn//Cu cells. The assembled Zn//I<sub>2</sub> full cells deliver excellent durability with a high capacity retention of 87.8% after 9000 cycles at 5.0 A g<sup>–1</sup>. This work establishes a viable weaving-inspired design strategy for natural polymer-based hydrogel electrolytes toward durable aqueous Zn–I<sub>2</sub> batteries and beyond.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"8 9-10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147439911","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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