Self-assembled monolayers (SAMs) have emerged as highly efficient hole transport layers for organic solar cells (OSCs). Nevertheless, the majority of SAM molecules are intrinsically amphiphilic and prone to aggregation in conventional alcohol-based processing solvents, leading to the formation of micellar nanoparticles. Such aggregation hampers the formation of dense and uniform SAM films on indium tin oxide (ITO) electrodes, thereby limiting charge extraction and device performance. Herein, we report a simple and broadly applicable cosolvent strategy to regulate the aggregation behavior of SAMs during solution processing. By introducing environmentally friendly cyclohexanol (CyOH) as a cosolvent with ethanol (EtOH), the aggregation of (2-(9H-carbazole-9-yl)) phosphonic acid (2PACz) is effectively suppressed, enabling fine control over its solution-state organization and interfacial assembly. This cosolvent system promotes the formation of dense, uniform, and well-ordered SAM films on ITO, resulting in improved interfacial energetics and enhanced device reproducibility and stability. As a result, OSCs based on PM6:BTP-eC9 achieves a champion power conversion efficiency (PCE) of 19.33%, compared to 18.26% for devices processed from pure EtOH. Notably, this strategy is compatible with multiple interfacial layer materials and photoactive systems, delivering a PCE exceeding 20% in the ternary D18:AQx-2F:BTP-eC9 system. This work demonstrates a green, versatile, and effective solvent-engineering approach for the design of high-performance OSCs.
自组装单层（SAMs）已成为有机太阳能电池（OSCs）中高效的空穴传输层。然而，大多数SAM分子本质上是两亲性的，在传统的醇基加工溶剂中容易聚集，导致胶束纳米颗粒的形成。这种聚集阻碍了在氧化铟锡（ITO）电极上形成致密均匀的SAM膜，从而限制了电荷提取和器件性能。在此，我们报告了一种简单而广泛适用的共溶剂策略来调节溶液处理过程中SAMs的聚集行为。通过引入环境友好型环己醇（CyOH）作为乙醇（EtOH）的助溶剂，可以有效抑制（2-（9h -咔唑-9-基））膦酸（2PACz）的聚集，从而精细控制其溶液态组织和界面组装。该共溶剂体系促进了ITO表面致密、均匀、有序的SAM膜的形成，从而改善了界面能量学，增强了器件的再现性和稳定性。因此，基于PM6: bp - ec9的OSCs实现了19.33%的冠军功率转换效率（PCE），而纯EtOH处理的器件为18.26%。值得注意的是，该策略与多种界面层材料和光活性体系兼容，在三元D18:AQx-2F:BTP-eC9体系中，PCE超过20%。这项工作展示了一种绿色、通用和有效的溶剂工程方法，用于设计高性能osc。
{"title":"Suppressing Aggregation in Self-Assembled Monolayers via an Environmentally Friendly Co-solvent Strategy for High-Performance Organic Solar Cells","authors":"Yaxiong Li,Xin Sun,Bin Feng,Linghui Qi,Wenqian Zhang,Longfei Jia,Sunsun Li,Ruizhi Zhang,Tugolbay Matisakov,Yuting Wang,Changlei Xia,Wenchao Zhao","doi":"10.1021/acssuschemeng.6c01237","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c01237","url":null,"abstract":"Self-assembled monolayers (SAMs) have emerged as highly efficient hole transport layers for organic solar cells (OSCs). Nevertheless, the majority of SAM molecules are intrinsically amphiphilic and prone to aggregation in conventional alcohol-based processing solvents, leading to the formation of micellar nanoparticles. Such aggregation hampers the formation of dense and uniform SAM films on indium tin oxide (ITO) electrodes, thereby limiting charge extraction and device performance. Herein, we report a simple and broadly applicable cosolvent strategy to regulate the aggregation behavior of SAMs during solution processing. By introducing environmentally friendly cyclohexanol (CyOH) as a cosolvent with ethanol (EtOH), the aggregation of (2-(9H-carbazole-9-yl)) phosphonic acid (2PACz) is effectively suppressed, enabling fine control over its solution-state organization and interfacial assembly. This cosolvent system promotes the formation of dense, uniform, and well-ordered SAM films on ITO, resulting in improved interfacial energetics and enhanced device reproducibility and stability. As a result, OSCs based on PM6:BTP-eC9 achieves a champion power conversion efficiency (PCE) of 19.33%, compared to 18.26% for devices processed from pure EtOH. Notably, this strategy is compatible with multiple interfacial layer materials and photoactive systems, delivering a PCE exceeding 20% in the ternary D18:AQx-2F:BTP-eC9 system. This work demonstrates a green, versatile, and effective solvent-engineering approach for the design of high-performance OSCs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147346689","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}
Organic cathodes hold promise for potassium-ion batteries (PIBs) but suffer from dissolution and poor conductivity. Here, we report a molecular grafting strategy to construct a stable β-PTCDA-D cathode by incorporating the nitrogen-rich heterocyclic linker 3,5-diamino-1,2,4-triazole (DAT) into perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). DAT incorporation promotes charge transfer and reduces the energy barrier for K+ storage. Meanwhile, the amidation reaction generates a robust molecule with extensive π-conjugation, strong hydrogen-bonding interactions, and enlarged interlayer spacing. These structural advantages improve electronic conductivity, suppress dissolution, and stabilize K+ intercalation/deintercalation, thereby maintaining structural integrity during cycling. As a result, β-PTCDA-D delivers a high reversible capacity of 100 mAh g–1 at 100 mA g–1, outstanding rate performance (75 mAh g–1 at 500 mA g–1), and excellent long-term stability with 76% retention after 200 cycles. Furthermore, a full cell paired with nanographite further demonstrates practical applicability. This work demonstrates the effectiveness of molecular interaction engineering in stabilizing small-molecule organic cathodes and provides a viable pathway for high-performance and sustainable PIBs.
有机阴极有望用于钾离子电池（PIBs），但存在溶解和导电性差的问题。本文报道了一种分子接枝策略，通过将富氮杂环连接剂3,5-二氨基-1,2,4-三唑（DAT）接枝到苝-3,4,9,10-四羧酸二酐（PTCDA）中来构建稳定的β-PTCDA-D阴极。DAT结合促进电荷转移，降低K+存储的能量垒。同时，酰胺化反应生成的分子具有广泛的π共轭、强的氢键相互作用和较大的层间距。这些结构优势提高了电子导电性，抑制了溶解，稳定了K+的插入/脱嵌，从而在循环过程中保持了结构的完整性。因此，β-PTCDA-D在100 mA g-1时具有100 mAh g-1的高可逆容量，出色的倍率性能（500 mA g-1时75 mAh g-1），并且在200次循环后具有76%的优异长期稳定性。此外，与纳米石墨烯配对的全电池进一步证明了其实用性。这项工作证明了分子相互作用工程在稳定小分子有机阴极方面的有效性，并为高性能和可持续的PIBs提供了可行的途径。
{"title":"A π-Conjugated Organic Cathode with Superior K+ Diffusion Kinetics for Potassium Ion Batteries","authors":"Erjin Zhang,Kelei Wu,Zhixin Liu,Peng Wang,Bing Hua,Jing Zhang,Yong Wang,Li Xu,Xuejiao Wang,Henan Li","doi":"10.1021/acssuschemeng.5c13867","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13867","url":null,"abstract":"Organic cathodes hold promise for potassium-ion batteries (PIBs) but suffer from dissolution and poor conductivity. Here, we report a molecular grafting strategy to construct a stable β-PTCDA-D cathode by incorporating the nitrogen-rich heterocyclic linker 3,5-diamino-1,2,4-triazole (DAT) into perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). DAT incorporation promotes charge transfer and reduces the energy barrier for K+ storage. Meanwhile, the amidation reaction generates a robust molecule with extensive π-conjugation, strong hydrogen-bonding interactions, and enlarged interlayer spacing. These structural advantages improve electronic conductivity, suppress dissolution, and stabilize K+ intercalation/deintercalation, thereby maintaining structural integrity during cycling. As a result, β-PTCDA-D delivers a high reversible capacity of 100 mAh g–1 at 100 mA g–1, outstanding rate performance (75 mAh g–1 at 500 mA g–1), and excellent long-term stability with 76% retention after 200 cycles. Furthermore, a full cell paired with nanographite further demonstrates practical applicability. This work demonstrates the effectiveness of molecular interaction engineering in stabilizing small-molecule organic cathodes and provides a viable pathway for high-performance and sustainable PIBs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147346662","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 : 2026-03-04DOI: 10.1021/acssuschemeng.5c14224
Welday Desta Weldu,Samuel Abidemi Oluwole,Solomon Owiredu,Nicole McGuire,Christian Agatemor
The electrochemical carbon dioxide reduction reaction (CO2RR) in water offers a sustainable pathway to mitigate carbon emissions while generating value-added chemicals. Most conventional CO2RR systems rely heavily on metal-based catalysts. Beyond traditional metal-based catalyst design, attention has increasingly shifted to understanding how the electrochemical microenvironment and the electrode–electrolyte interface influence CO2RR. Ionic liquids (ILs), widely regarded as green solvents, have previously been employed as electrolytes or cocatalysts in metal-catalyzed systems. Yet, the ability of ILs to facilitate CO2RR at metal-free interfaces in aqueous media remains underexplored. Here, we demonstrate that ILs polarize CO2 and facilitate CO2 electrochemical response at a glassy carbon interface under aqueous conditions, while simultaneously functioning as electrolytes. Spectroscopic, electrochemical, and computational analyses reveal that ILs interact with CO2, thereby increasing its dipole moment. This interaction suggests a favorable environment for CO2 polarization that correlates with the observed electrochemical response. The response efficiency depends on the chemical identity of the ILs, highlighting the tunability of this IL-based system. These findings redefine the functional role of ILs in CO2RR, establishing IL-induced molecular polarization as a potential strategy for promoting the reactivity of otherwise inert molecules. More broadly, this work introduces IL-driven dipole modulation as a general approach for enabling reactivity of nonpolar small molecules, with implications for sustainable chemical synthesis.
{"title":"Ionic Liquids as Interfacial Media for Metal-Free Electrochemical CO2 Reduction in Water","authors":"Welday Desta Weldu,Samuel Abidemi Oluwole,Solomon Owiredu,Nicole McGuire,Christian Agatemor","doi":"10.1021/acssuschemeng.5c14224","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c14224","url":null,"abstract":"The electrochemical carbon dioxide reduction reaction (CO2RR) in water offers a sustainable pathway to mitigate carbon emissions while generating value-added chemicals. Most conventional CO2RR systems rely heavily on metal-based catalysts. Beyond traditional metal-based catalyst design, attention has increasingly shifted to understanding how the electrochemical microenvironment and the electrode–electrolyte interface influence CO2RR. Ionic liquids (ILs), widely regarded as green solvents, have previously been employed as electrolytes or cocatalysts in metal-catalyzed systems. Yet, the ability of ILs to facilitate CO2RR at metal-free interfaces in aqueous media remains underexplored. Here, we demonstrate that ILs polarize CO2 and facilitate CO2 electrochemical response at a glassy carbon interface under aqueous conditions, while simultaneously functioning as electrolytes. Spectroscopic, electrochemical, and computational analyses reveal that ILs interact with CO2, thereby increasing its dipole moment. This interaction suggests a favorable environment for CO2 polarization that correlates with the observed electrochemical response. The response efficiency depends on the chemical identity of the ILs, highlighting the tunability of this IL-based system. These findings redefine the functional role of ILs in CO2RR, establishing IL-induced molecular polarization as a potential strategy for promoting the reactivity of otherwise inert molecules. More broadly, this work introduces IL-driven dipole modulation as a general approach for enabling reactivity of nonpolar small molecules, with implications for sustainable chemical synthesis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147346685","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 : 2026-03-04DOI: 10.1021/acssuschemeng.5c12063
Min Zhang,I-Shin Chang,Bowen Li,Haoran Zhang,Jing Wu
Rapid expansion of electric vehicles (EVs) has led to a surge in retired batteries. It is critical to establish an efficient and sustainable recycling system of retired electric vehicle batteries (EVBs) for resource circularity and carbon reduction. As the world’s largest EV manufacturer and market, China is in urgent need of systematic governance of the retired EVB recycling industry. Although a growing body of research has examined the EVB recycling industry, a systematic review of the recycling system is still lacking. From the perspective of the industrial chain, this study integrates field research, in-depth interviews, multicase analysis, and systematic literature review to provide a comprehensive assessment of China’s EVB recycling system. It first maps the structural configuration and developmental landscape of the EVB recycling industry. Second, from the perspective of stakeholders, dominant business models, manufacturer-led, third-party-led, and alliance-led, are examined in terms of operational mechanisms and profit logic. Further, a PESTEL-based multimismatch framework is proposed to identify nine structural barriers of the EVB recycling industry, from collection to recycling. To address these challenges, a multistakeholder collaborative pathway is proposed, emphasizing the integration of policy, industry, and societal factors to establish a data-driven governance network that incorporates institutional supply, standard refinement, responsibility allocation, and public participation. This study offers insights for advancing the sustainable EVB recycling industry in China and beyond and contributes to the achievement of global climate goals.
{"title":"Study on Retired Electric Vehicle Battery Recycling Industry via Business Models, Structural Barriers, and Synergistic Pathways","authors":"Min Zhang,I-Shin Chang,Bowen Li,Haoran Zhang,Jing Wu","doi":"10.1021/acssuschemeng.5c12063","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12063","url":null,"abstract":"Rapid expansion of electric vehicles (EVs) has led to a surge in retired batteries. It is critical to establish an efficient and sustainable recycling system of retired electric vehicle batteries (EVBs) for resource circularity and carbon reduction. As the world’s largest EV manufacturer and market, China is in urgent need of systematic governance of the retired EVB recycling industry. Although a growing body of research has examined the EVB recycling industry, a systematic review of the recycling system is still lacking. From the perspective of the industrial chain, this study integrates field research, in-depth interviews, multicase analysis, and systematic literature review to provide a comprehensive assessment of China’s EVB recycling system. It first maps the structural configuration and developmental landscape of the EVB recycling industry. Second, from the perspective of stakeholders, dominant business models, manufacturer-led, third-party-led, and alliance-led, are examined in terms of operational mechanisms and profit logic. Further, a PESTEL-based multimismatch framework is proposed to identify nine structural barriers of the EVB recycling industry, from collection to recycling. To address these challenges, a multistakeholder collaborative pathway is proposed, emphasizing the integration of policy, industry, and societal factors to establish a data-driven governance network that incorporates institutional supply, standard refinement, responsibility allocation, and public participation. This study offers insights for advancing the sustainable EVB recycling industry in China and beyond and contributes to the achievement of global climate goals.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"199 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147346684","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 : 2026-03-04DOI: 10.1021/acssuschemeng.5c14049
Peng Guo, HongWei Li, BoYu Huang, Dong Ji, GuiXian Li, XinHong Zhao
High-performance catalysts for the methanol oxidation reaction (MOR) are critical for advancing direct methanol fuel cells. Here, we report a three-dimensionally ordered macroporous superstructure of nitrogen-doped hierarchical porous carbon (NHPC) implanted with ultrafine Pd nanoclusters (∼1.8 nm) as a highly efficient electrocatalytic micronano reactor (Pd/NHPC). Constructed via nanocasting of ZIF-8 on polystyrene colloidal crystals, followed by the confined growth of Pd, this architecture features interconnected macropores that maximize mass transport and active-site exposure. In alkaline media (1.0 M KOH + 1.0 M CH3OH), Pd/NHPC achieves a mass activity of 7383 mA mgPd–1─surpassing commercial Pt/C and Pd/C by factors of 4.09 and 3.80, respectively. It exhibits exceptional stability, retaining 95.0% activity after 500 cycles at 200 mV s–1, and delivering 2373 mA mgPd–1 after 7200 s chronoamperometry. Mechanistic studies reveal that the hierarchical porosity accelerates reactant diffusion/intermediate desorption, while optimized nitrogen configurations (pyridinic/pyrrolic/graphitic-N) enhance metal–support interaction, enrich electron density on Pd0 sites, and facilitate a direct (CO-poisoning-free) MOR pathway. This work establishes a paradigm for designing stable, high-activity nanocatalysts through synergistic structural and electronic engineering.
高性能的甲醇氧化反应催化剂是推进甲醇直接燃料电池发展的关键。在这里，我们报道了一种三维有序的大孔上层结构，氮掺杂的分层多孔碳（NHPC）植入超细Pd纳米团簇（~ 1.8 nm），作为高效的电催化微纳米反应器（Pd/NHPC）。通过在聚苯乙烯胶体晶体上纳米浇铸ZIF-8，然后限制Pd的生长，该结构具有相互连接的大孔，最大限度地提高了质量传输和活性位点暴露。在碱性介质（1.0 M KOH + 1.0 M CH3OH）中，Pd/NHPC的质量活度达到7383 mA mgPd-1，分别比商业Pt/C和Pd/C高出4.09和3.80倍。它具有优异的稳定性，在200 mV s - 1下循环500次后保持95.0%的活性，在7200 s计时电流后提供2373 mA的mgPd-1。机制研究表明，分层孔隙加速了反应物扩散/中间产物脱附，而优化的氮构型（吡啶/吡啶/石墨- n）增强了金属-载体相互作用，增加了Pd0位点上的电子密度，促进了直接（co -free） MOR途径。这项工作为通过协同结构和电子工程设计稳定、高活性的纳米催化剂建立了一个范例。
{"title":"Three-Dimensionally Ordered Macroporous Superstructure of Nitrogen-Doped Hierarchical Porous Carbon Implanted with Ultrafine Pd Nanoclusters for the Efficient Methanol Oxidation Reaction","authors":"Peng Guo, HongWei Li, BoYu Huang, Dong Ji, GuiXian Li, XinHong Zhao","doi":"10.1021/acssuschemeng.5c14049","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c14049","url":null,"abstract":"High-performance catalysts for the methanol oxidation reaction (MOR) are critical for advancing direct methanol fuel cells. Here, we report a three-dimensionally ordered macroporous superstructure of nitrogen-doped hierarchical porous carbon (NHPC) implanted with ultrafine Pd nanoclusters (∼1.8 nm) as a highly efficient electrocatalytic micronano reactor (Pd/NHPC). Constructed via nanocasting of ZIF-8 on polystyrene colloidal crystals, followed by the confined growth of Pd, this architecture features interconnected macropores that maximize mass transport and active-site exposure. In alkaline media (1.0 M KOH + 1.0 M CH<sub>3</sub>OH), Pd/NHPC achieves a mass activity of 7383 mA mg<sub>Pd</sub><sup>–1</sup>─surpassing commercial Pt/C and Pd/C by factors of 4.09 and 3.80, respectively. It exhibits exceptional stability, retaining 95.0% activity after 500 cycles at 200 mV s<sup>–1</sup>, and delivering 2373 mA mg<sub>Pd</sub><sup>–1</sup> after 7200 s chronoamperometry. Mechanistic studies reveal that the hierarchical porosity accelerates reactant diffusion/intermediate desorption, while optimized nitrogen configurations (pyridinic/pyrrolic/graphitic-N) enhance metal–support interaction, enrich electron density on Pd<sup>0</sup> sites, and facilitate a direct (CO-poisoning-free) MOR pathway. This work establishes a paradigm for designing stable, high-activity nanocatalysts through synergistic structural and electronic engineering.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Agricultural waste is a renewable yet underutilized resource for producing binderless biocomposites. This study develops biocomposite boards from blended eggplant (ESP) and tomato (TSP) stalk fibers using single-material boards as references. Homogeneous and sandwich structures were fabricated at identical fiber ratios (75:25, 50:50, and 25:75) to distinguish compositional effects from structural contributions and reveal synergistic interactions. The optimal ESP/TSP ratio of 25:75 yielded a bending strength of 80.59 MPa in homogeneous boards and a tensile strength of 41.11 MPa in sandwich boards, which also showed superior water resistance. The 75:25 homogeneous board exhibited an initial water contact angle of 136.46°, with all samples maintaining a hydrophobicity of >100° after 10 s. Thermal conductivities of 0.0886–0.1076 W·m–1·K–1 indicated excellent insulation performance, and combustion tests demonstrated controllable burning behavior with potential for end-of-life energy recovery. The sandwich-structured biocomposite boards exhibited significantly enhanced tensile strength and water resistance due to effective interlayer synergy. Overall, synergistic optimization of the fiber ratio and structural configuration enabled high-performance adhesive-free biocomposites and provided a sustainable route for converting agricultural waste into functional materials for architectural and furniture manufacturing applications.
{"title":"Binderless Biocomposite Boards from Tomato and Eggplant Stalks: Synergistic Effects of Fiber Ratio and Structural Design","authors":"Hailun Fan, Xiulun Wang, Changqing Cai, Jianzhong Sun, Jun Liu, Tingting Wu","doi":"10.1021/acssuschemeng.5c12870","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12870","url":null,"abstract":"Agricultural waste is a renewable yet underutilized resource for producing binderless biocomposites. This study develops biocomposite boards from blended eggplant (ESP) and tomato (TSP) stalk fibers using single-material boards as references. Homogeneous and sandwich structures were fabricated at identical fiber ratios (75:25, 50:50, and 25:75) to distinguish compositional effects from structural contributions and reveal synergistic interactions. The optimal ESP/TSP ratio of 25:75 yielded a bending strength of 80.59 MPa in homogeneous boards and a tensile strength of 41.11 MPa in sandwich boards, which also showed superior water resistance. The 75:25 homogeneous board exhibited an initial water contact angle of 136.46°, with all samples maintaining a hydrophobicity of >100° after 10 s. Thermal conductivities of 0.0886–0.1076 W·m<sup>–1</sup>·K<sup>–1</sup> indicated excellent insulation performance, and combustion tests demonstrated controllable burning behavior with potential for end-of-life energy recovery. The sandwich-structured biocomposite boards exhibited significantly enhanced tensile strength and water resistance due to effective interlayer synergy. Overall, synergistic optimization of the fiber ratio and structural configuration enabled high-performance adhesive-free biocomposites and provided a sustainable route for converting agricultural waste into functional materials for architectural and furniture manufacturing applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"70 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334458","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 : 2026-03-03DOI: 10.1021/acssuschemeng.5c12510
Shelby R. Watson-Sanders, Kendra Day Johnson, Timothy Taylor, Sarah Barber, Mark D. Dadmun
Polyethylene terephthalate (PET) is a widely used material in single-use consumer products with increasing production demands each year. This study examines a more sustainable method to upcycle PET to produce telechelic oligomers that can function as macromonomers for polymerization or can be transformed into value-added products. The research examines the impact of annealing PET near its melting point on the evolution of the chain structure during depolymerization. These results show that this annealing provides a simple and energy-efficient protocol to successfully obtain dihydroxy-terminated oligomers from consumer waste, with varying molecular weights that are guided by the predepolymerization annealing time. Dihydroxy-terminated PET oligomers are isolated from the depolymerization process more quickly if the PET is annealed before depolymerization, and the molecular weight of the telechelic oligomers can be controlled by adjusting the annealing time. This is because longer annealing times yield higher-molecular-weight precursors with enhanced chemically reactive tie chains formed from stretched amorphous regions. However, increased crystallinity prior to depolymerization, as indicated by differential scanning calorimetry, does not alter the molecular weight of oligomers isolated from depolymerization. The production of the dihydroxy-terminated oligomers also leads to the fragmentation of PET flakes into a powder, providing a visual indication of the isolation of telechelic oligomers via glycolysis. It is hypothesized that the PET flakes fracture when most of the tie chains are severed. Consequently, dihydroxy-terminated oligomers can be more promptly obtained with predepolymerization annealing, reducing reaction time, and eliminating the need for postdepolymerization functionalization steps, thereby improving the overall sustainability of PET upcycling.
{"title":"Energy-Efficient Upcycling of Waste Poly(ethylene terephthalate) via Pre-Annealing-Induced Formation of Reactive Telechelic Oligomers","authors":"Shelby R. Watson-Sanders, Kendra Day Johnson, Timothy Taylor, Sarah Barber, Mark D. Dadmun","doi":"10.1021/acssuschemeng.5c12510","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12510","url":null,"abstract":"Polyethylene terephthalate (PET) is a widely used material in single-use consumer products with increasing production demands each year. This study examines a more sustainable method to upcycle PET to produce telechelic oligomers that can function as macromonomers for polymerization or can be transformed into value-added products. The research examines the impact of annealing PET near its melting point on the evolution of the chain structure during depolymerization. These results show that this annealing provides a simple and energy-efficient protocol to successfully obtain dihydroxy-terminated oligomers from consumer waste, with varying molecular weights that are guided by the predepolymerization annealing time. Dihydroxy-terminated PET oligomers are isolated from the depolymerization process more quickly if the PET is annealed before depolymerization, and the molecular weight of the telechelic oligomers can be controlled by adjusting the annealing time. This is because longer annealing times yield higher-molecular-weight precursors with enhanced chemically reactive tie chains formed from stretched amorphous regions. However, increased crystallinity prior to depolymerization, as indicated by differential scanning calorimetry, does not alter the molecular weight of oligomers isolated from depolymerization. The production of the dihydroxy-terminated oligomers also leads to the fragmentation of PET flakes into a powder, providing a visual indication of the isolation of telechelic oligomers via glycolysis. It is hypothesized that the PET flakes fracture when most of the tie chains are severed. Consequently, dihydroxy-terminated oligomers can be more promptly obtained with predepolymerization annealing, reducing reaction time, and eliminating the need for postdepolymerization functionalization steps, thereby improving the overall sustainability of PET upcycling.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334459","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 : 2026-03-03DOI: 10.1021/acssuschemeng.5c12976
Yi Liao, Fenghang Zhao, Shiqi Zeng, Sichen Li, Yanjun Ye, Ke Jiang, Hui Xiao, Yuzhu Chen
Soy protein (SP) adhesives represent a promising environmentally friendly binder; however, their practical application is hindered by inherent limitations, including poor water resistance, low mechanical strength, and vulnerability to microbial degradation. In this study, we synthesized a novel ZIF-8-Ag composite using a straightforward room-temperature method and incorporated it into soy protein isolate (SPI) to create a high-performance biobased adhesive. Morphological and structural analyses confirmed that Ag nanoparticles were successfully immobilized on the ZIF-8 framework without compromising its structural integrity. SPI-based adhesives modified with varying ZIF-8-Ag loadings (0–1.0 g per 10 g SPI) demonstrated significantly enhanced viscosity, bonding strength, water resistance, thermal stability, and mold resistance. The optimal performance was achieved with a ZIF-8-Ag loading of 0.8 g, where the dry and wet shear strengths reached 4.9 and 3.72 MPa, reflecting improvements of 236.49% and 324.21%, respectively, compared to the unmodified SPI adhesive. Antimold stability increased by 143%, resulting in a residual rate of 89.17%. This enhancement is attributed to the synergistic interaction between Ag+ and Zn2+ ions with functional groups in SPI, which facilitates the formation of a denser cross-linked network. This network restricts molecular mobility and establishes a protective barrier against moisture and microorganisms. This study presents a sustainable development strategy for designing high-performance biobased adhesives.
大豆蛋白（SP）粘合剂是一种很有前途的环保粘合剂；然而，它们的实际应用受到固有限制的阻碍，包括耐水性差、机械强度低、易被微生物降解。在这项研究中，我们使用简单的室温方法合成了一种新的ZIF-8-Ag复合材料，并将其掺入大豆分离蛋白（SPI）中，以创建高性能的生物基粘合剂。形态和结构分析证实，银纳米颗粒成功地固定在ZIF-8框架上，而不影响其结构完整性。用不同的ZIF-8-Ag负载（每10 g SPI 0-1.0 g）改性的SPI基粘合剂显示出显著增强的粘度、粘接强度、耐水性、热稳定性和抗霉菌性。ZIF-8-Ag添加量为0.8 g时，其干、湿抗剪强度分别达到4.9 MPa和3.72 MPa，比未改性的SPI胶粘剂分别提高了236.49%和324.21%。锑的稳定性提高了143%，残余率为89.17%。这种增强归因于SPI中Ag+和Zn2+离子与官能团之间的协同相互作用，这有助于形成更密集的交联网络。这个网络限制了分子的流动性，并建立了防止水分和微生物的保护屏障。本研究提出了设计高性能生物基胶粘剂的可持续发展策略。
{"title":"Dual-Metal Synergy in Soy Protein Adhesives: Silver and Zinc Ions Co-Anchor on a Nanoporous Framework for Enhanced Bonding, Water Resistance, and Mold Resistance","authors":"Yi Liao, Fenghang Zhao, Shiqi Zeng, Sichen Li, Yanjun Ye, Ke Jiang, Hui Xiao, Yuzhu Chen","doi":"10.1021/acssuschemeng.5c12976","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12976","url":null,"abstract":"Soy protein (SP) adhesives represent a promising environmentally friendly binder; however, their practical application is hindered by inherent limitations, including poor water resistance, low mechanical strength, and vulnerability to microbial degradation. In this study, we synthesized a novel ZIF-8-Ag composite using a straightforward room-temperature method and incorporated it into soy protein isolate (SPI) to create a high-performance biobased adhesive. Morphological and structural analyses confirmed that Ag nanoparticles were successfully immobilized on the ZIF-8 framework without compromising its structural integrity. SPI-based adhesives modified with varying ZIF-8-Ag loadings (0–1.0 g per 10 g SPI) demonstrated significantly enhanced viscosity, bonding strength, water resistance, thermal stability, and mold resistance. The optimal performance was achieved with a ZIF-8-Ag loading of 0.8 g, where the dry and wet shear strengths reached 4.9 and 3.72 MPa, reflecting improvements of 236.49% and 324.21%, respectively, compared to the unmodified SPI adhesive. Antimold stability increased by 143%, resulting in a residual rate of 89.17%. This enhancement is attributed to the synergistic interaction between Ag<sup>+</sup> and Zn<sup>2+</sup> ions with functional groups in SPI, which facilitates the formation of a denser cross-linked network. This network restricts molecular mobility and establishes a protective barrier against moisture and microorganisms. This study presents a sustainable development strategy for designing high-performance biobased adhesives.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"130 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358819","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 practical application of hydrogel-based Al–air batteries is severely hampered by the intrinsic trade-off between mechanical robustness and ionic conductivity, along with uncontrolled water-induced parasitic reactions. In this study, we report a bioinspired triply hierarchical hydrogel electrolyte. Through the in situ polymerization of poly(acrylic acid) within a natural loofah sponge, macro-micro-nano hierarchical pores are developed, and a robust quasi-solid polymer electrolyte is obtained for high-performance flexible Al–air batteries. The composite hydrogel exhibits a remarkable mechanical enhancement, with a tensile strength ∼70.69 times greater than that of pure poly(acrylic acid). Simultaneously, a high ionic conductivity of 333.98 mS/cm is obtained, owing to the synergistic effect of efficient water retention and rapid ion transport within the triply hierarchical pores. Besides, the transport of free water molecules is regulated intelligently, suppressing the hydrogen evolution reaction of the Al anode with an impressive anticorrosion efficiency of 63.55%. Furthermore, the flexible Al–air battery using the proposed hydrogel delivers a specific capacity of 1805.98 mAh/g at 5 mA/cm2 and a peak power density of 52.65 mW/cm2. The cyclic discharge longevity of the battery reaches 2.05 times that of pure poly(acrylic acid). Remarkably, the battery maintains stable operation even at −20 °C, showcasing excellent adaptability to harsh environments. The composite hydrogel offers a green and sustainable strategy for developing robust hydrogel electrolytes for advanced flexible energy storage systems under extreme conditions.
{"title":"Bioinspired Triply Hierarchical Hydrogel Electrolyte for Wide-Temperature-Adaptive Flexible Al–Air Batteries","authors":"Manhui Wei, Zhenxiong Wang, Pengfei Zhang, Hengwei Wang, Kaichuang Zhang, Keliang Wang","doi":"10.1021/acssuschemeng.6c00758","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00758","url":null,"abstract":"The practical application of hydrogel-based Al–air batteries is severely hampered by the intrinsic trade-off between mechanical robustness and ionic conductivity, along with uncontrolled water-induced parasitic reactions. In this study, we report a bioinspired triply hierarchical hydrogel electrolyte. Through the in situ polymerization of poly(acrylic acid) within a natural loofah sponge, macro-micro-nano hierarchical pores are developed, and a robust quasi-solid polymer electrolyte is obtained for high-performance flexible Al–air batteries. The composite hydrogel exhibits a remarkable mechanical enhancement, with a tensile strength ∼70.69 times greater than that of pure poly(acrylic acid). Simultaneously, a high ionic conductivity of 333.98 mS/cm is obtained, owing to the synergistic effect of efficient water retention and rapid ion transport within the triply hierarchical pores. Besides, the transport of free water molecules is regulated intelligently, suppressing the hydrogen evolution reaction of the Al anode with an impressive anticorrosion efficiency of 63.55%. Furthermore, the flexible Al–air battery using the proposed hydrogel delivers a specific capacity of 1805.98 mAh/g at 5 mA/cm<sup>2</sup> and a peak power density of 52.65 mW/cm<sup>2</sup>. The cyclic discharge longevity of the battery reaches 2.05 times that of pure poly(acrylic acid). Remarkably, the battery maintains stable operation even at −20 °C, showcasing excellent adaptability to harsh environments. The composite hydrogel offers a green and sustainable strategy for developing robust hydrogel electrolytes for advanced flexible energy storage systems under extreme conditions.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358882","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 : 2026-03-03DOI: 10.1021/acssuschemeng.5c12327
Junfeng Zeng, Hongli Zhu, Jinna Wang, Yan Duan, Yan Zhang, Hussein A. Younus, Wenpeng Ni, Shiguo Zhang
Conductive metal–organic frameworks (c-MOFs) represent a promising platform for designing bifunctional electrocatalysts toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, identifying optimal compositions through conventional “trial-and-error” approaches remains formidable due to their vast compositional complexity. Here, we present a theoretical investigation that integrates high-throughput density functional theory calculations with machine learning to explore entropy-driven design strategies in 2,3,6,7,10,11-hexaimino-triphenylene (HITP)-based c-MOFs. Systems incorporating Fe, Co, Ni, Cu, and Zn metal centers were found to be thermodynamically and electrochemically stable. Screening 75 potential active sites across 35 M3(HITP)2 frameworks identified CoCoZn(HITP)2 as the most efficient bifunctional catalyst with a total overpotential of 0.39 V. Counterintuitively, bimetallic configurations systematically outperformed their higher-entropy trimetallic analogues, revealing that optimal electronic synergy supersedes configurational entropy in governing catalytic efficiency. Electronic structure analysis revealed that the near-ideal orbital energy alignment between Fe d-states and H s-states renders Fe sites intrinsically favorable for HER. Concurrently, the Co d-band center in CoCoZn(HITP)2 suffer an downshift and enhanced electron transfer to *OH intermediates, thus strengthening OER activity. Finally, the stacking ensemble machine learning framework provides a reliable model for bifunctional activity prediction (R2 = 0.907), identifying the combination of electron affinity and valence electron count as the most critical activity descriptor.
{"title":"Heteromultimetallic Conductive Metal–Organic Framework as Bifunctional Electrocatalyst for Water Splitting: A Combined DFT and Machine Learning Study","authors":"Junfeng Zeng, Hongli Zhu, Jinna Wang, Yan Duan, Yan Zhang, Hussein A. Younus, Wenpeng Ni, Shiguo Zhang","doi":"10.1021/acssuschemeng.5c12327","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12327","url":null,"abstract":"Conductive metal–organic frameworks (c-MOFs) represent a promising platform for designing bifunctional electrocatalysts toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, identifying optimal compositions through conventional “trial-and-error” approaches remains formidable due to their vast compositional complexity. Here, we present a theoretical investigation that integrates high-throughput density functional theory calculations with machine learning to explore entropy-driven design strategies in 2,3,6,7,10,11-hexaimino-triphenylene (HITP)-based c-MOFs. Systems incorporating Fe, Co, Ni, Cu, and Zn metal centers were found to be thermodynamically and electrochemically stable. Screening 75 potential active sites across 35 M<sub>3</sub>(HITP)<sub>2</sub> frameworks identified CoCoZn(HITP)<sub>2</sub> as the most efficient bifunctional catalyst with a total overpotential of 0.39 V. Counterintuitively, bimetallic configurations systematically outperformed their higher-entropy trimetallic analogues, revealing that optimal electronic synergy supersedes configurational entropy in governing catalytic efficiency. Electronic structure analysis revealed that the near-ideal orbital energy alignment between Fe d-states and H s-states renders Fe sites intrinsically favorable for HER. Concurrently, the Co d-band center in CoCoZn(HITP)<sub>2</sub> suffer an downshift and enhanced electron transfer to *OH intermediates, thus strengthening OER activity. Finally, the stacking ensemble machine learning framework provides a reliable model for bifunctional activity prediction (<i>R</i><sup>2</sup> = 0.907), identifying the combination of electron affinity and valence electron count as the most critical activity descriptor.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"35 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334457","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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